U.S. patent number 10,845,703 [Application Number 15/528,037] was granted by the patent office on 2020-11-24 for film-forming composition containing silicone having crosslinking reactivity.
This patent grant is currently assigned to NISSAN CHEMICAL INDUSTRIES, LTD.. The grantee listed for this patent is NISSAN CHEMICAL INDUSTRIES, LTD.. Invention is credited to Masahisa Endo, Makoto Nakajima, Kenji Takase, Hiroyuki Wakayama.
View All Diagrams
United States Patent |
10,845,703 |
Nakajima , et al. |
November 24, 2020 |
Film-forming composition containing silicone having crosslinking
reactivity
Abstract
A film-forming composition having favorable effects such as
curability and embeddability and resist underlayer film for use in
lithography process for semiconductor devices. The film-forming
composition including, as silane, hydrolyzable silane, hydrolysis
product thereof, or hydrolysis-condensation product thereof,
wherein hydrolyzable silane includes hydrolyzable silane of Formula
(1): R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4-(a+b) Formula (1)
in Formula (1), R.sup.1 is organic group of Formula (2) and is
bonded to silicon atom through Si--C bond: ##STR00001## The
film-forming composition, wherein the hydrolyzable silane is
combination of hydrolyzable silane of Formula (1) with another
hydrolyzable silane, wherein other hydrolyzable silane is at least
one selected from group made of hydrolyzable silane of Formula (3):
R.sup.7.sub.cSi(R.sup.8).sub.4-c Formula (3) and hydrolyzable
silane of Formula (4):
R.sup.9.sub.dSi(R.sup.10).sub.3-d.sub.2Y.sub.e Formula (4) Resist
underlayer film, obtained by applying the resist underlayer
film-forming composition on semiconductor substrate and baking.
Inventors: |
Nakajima; Makoto (Toyama,
JP), Takase; Kenji (Funabashi, JP), Endo;
Masahisa (Toyama, JP), Wakayama; Hiroyuki
(Toyama, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
NISSAN CHEMICAL INDUSTRIES, LTD. |
Tokyo |
N/A |
JP |
|
|
Assignee: |
NISSAN CHEMICAL INDUSTRIES,
LTD. (Tokyo, JP)
|
Family
ID: |
1000005202527 |
Appl.
No.: |
15/528,037 |
Filed: |
November 9, 2015 |
PCT
Filed: |
November 09, 2015 |
PCT No.: |
PCT/JP2015/081476 |
371(c)(1),(2),(4) Date: |
May 18, 2017 |
PCT
Pub. No.: |
WO2016/080226 |
PCT
Pub. Date: |
May 26, 2016 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20180335698 A1 |
Nov 22, 2018 |
|
Foreign Application Priority Data
|
|
|
|
|
Nov 19, 2014 [JP] |
|
|
2014-234590 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G
77/14 (20130101); G03F 7/162 (20130101); C08G
77/18 (20130101); C09D 183/00 (20130101); C09D
183/06 (20130101); G03F 7/168 (20130101); C07F
7/1804 (20130101); H01L 21/027 (20130101); G03F
7/322 (20130101); H01L 21/0274 (20130101); G03F
7/38 (20130101); G03F 7/2004 (20130101); G03F
7/11 (20130101) |
Current International
Class: |
G03F
7/11 (20060101); C07F 7/18 (20060101); C08G
77/14 (20060101); H01L 21/027 (20060101); C09D
183/00 (20060101); C08G 77/18 (20060101); G03F
7/38 (20060101); C09D 183/06 (20060101); G03F
7/16 (20060101); G03F 7/20 (20060101); G03F
7/32 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
1908472 |
|
Apr 2008 |
|
EP |
|
H03-275769 |
|
Dec 1991 |
|
JP |
|
H11-060735 |
|
Mar 1999 |
|
JP |
|
2009-537645 |
|
Oct 2009 |
|
JP |
|
2010100591 |
|
May 2010 |
|
JP |
|
2011-170059 |
|
Sep 2011 |
|
JP |
|
2006/126406 |
|
Nov 2006 |
|
WO |
|
2007/131985 |
|
Nov 2007 |
|
WO |
|
Other References
Oct. 5, 2017 Written Opinion issued in Singapore Patent Application
No. 11201704070S. cited by applicant .
Leigh, William J., "Intramolecular Nucleophile-Induced
Photorearrangements and Silene Formation from an
o-(Methoxymethyl)phenylsilacyclobutane", Journal of American
Chemical Society, 2003, pp. 8096-8097. cited by applicant .
Schoeller, Wolfgang W., "Pentacoordination at Fluoro-Substituted
Silanes by Weak Lewis Donor Addition," European Journal of
Inorganic Chemistry, 2000, pp. 375-381. cited by applicant .
Mix, A. et al., "2-(Alkoxymethyl) phenylsilicon compounds: the
search for pentacoordination," Journal of Organometallic Chemistry,
1996, pp. 177-183. cited by applicant .
Jul. 8, 2013, Reigstry (STN), CAS Registry No. 1443325-86-7. cited
by applicant .
Kostikov, Alexey P. et al., "Oxalic Acid Supported
Si-18F-Radiofluorination: One-Step Radiosynthesis of N-Succinimidyl
3-(Di-tert-butyl[18F]fluorosilyl) benzoate ([18F]SiFB) for Protein
Labeling," Bioconjugate Chemistry, 2012, pp. 106-114. cited by
applicant .
Berends, Ljuba Iovkova et al., "t-Bu2SiF-Derivatized D2-Receptor
Ligands: The First SiFA-Containing Small Molecule Radiotracers for
Target-Specific PET-Imaging," Molecules, 2011, vol. 16, pp.
7458-7479. cited by applicant .
Iovkova, Ljuba et al., "para-Functionalized
Aryl-di-tert-butylfluorosilanes as Potential Labeling Synthons for
18F Radiopharmaceuticals," Chemistry, 2009, pp. 2140-2147. cited by
applicant .
Hohne, Aileen et al., "Organofluorosilanes as Model Compounds for
18F-Labeled Silicon-Based PET Tracers and their Hydrolytic
Stability: Experimental Data and Theoretical Calculations
(PET=Positron Emission Tomography)", Chemistry--A European Journal,
2009, pp. 3736-3743. cited by applicant .
Bockholt, Andreas et al., "Neutral and Catonic Silicon Species
Containing Aryl-OCO- or Aryl-SCS-Type Pincer Ligands: Synthesis,
Structure, Bonding, and Comparison with Aryl-NCN Systems,"
Zeitschrift fuer Anorganishe und Allgemine Chemie, 2009, vol. 635,
pp. 1326-1334. cited by applicant .
Feb. 16, 2016 Written Opinion issued in International Patent
Application No. PCT/JP2015/081476. cited by applicant .
Feb. 16, 2016 International Search Report issued in International
Patent Application No. PCT/JP2015/081476. cited by applicant .
May 25, 2018 Extended European Search Report issued in European
Application No. 15 86 0187.2. cited by applicant.
|
Primary Examiner: Woldegeorgis; Ermias T
Attorney, Agent or Firm: Oliff PLC
Claims
The invention claimed is:
1. A film-forming composition, the composition comprising: as a
silane, a hydrolyzable silane, a hydrolysis product thereof, or a
hydrolysis-condensation product thereof, wherein the hydrolyzable
silane includes a hydrolyzable silane of Formula (1):
R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4-(a+b) Formula (1)
wherein R.sup.1 is an organic group of Formula (2) and is bonded to
a silicon atom through a Si--C bond or a Si--O bond: ##STR00044##
wherein R.sup.4 is a hydrogen atom, a C.sub.1-10 alkyl group, or an
acyl group, R.sup.5 is a hydrogen atom, a C.sub.1-10 alkyl group,
or a C.sub.1-10 alkyl group having a C.sub.1-10 alkoxy group,
R.sup.6 is a C.sub.1-10 alkyl group, n1 is an integer of 0 to 10,
n2 is an integer of 0 or 1, n3, n4 and n5 are integers, where n3
satisfies 1.ltoreq.n3.ltoreq.5, n4 satisfies 0.ltoreq.n4.ltoreq.4,
and n5 satisfies 0.ltoreq.n5.ltoreq.4, k1 is a bond end with a
silicon atom when n1 is an integer of 1 to 10, k2 is a bond end
with a silicon atom when n1 is 0 and n2 is 1, and k3 is a bond end
with a silicon atom when n1 and n2 are 0; R.sup.2 is an alkyl
group, an aryl group, a halogenated alkyl group, a halogenated aryl
group, an alkoxyaryl group, an alkenyl group, or an organic group
having an epoxy group, an acryloyl group, a methacryloyl group, a
mercapto group, an amino group, or a cyano group, or a combination
thereof, and is bonded to a silicon atom through a Si--C bond;
R.sup.3 is an alkoxy group, an acyloxy group, or a halogen group; a
is an integer of 1; b is an integer of 0 to 2; and a+b is an
integer of 1 to 3.
2. The film-forming composition according to claim 1, wherein the
hydrolyzable silane is a combination of the hydrolyzable silane of
Formula (1) with another hydrolyzable silane, in which the other
hydrolyzable silane is at least one hydrolyzable silane selected
from the group consisting of: a hydrolyzable silane of Formula (3):
R.sup.7.sub.cSi(R.sup.8).sub.4-c Formula (3) wherein R.sup.7 is an
alkyl group, an aryl group, a halogenated alkyl group, a
halogenated aryl group, an alkoxyalkyl group, an alkoxyaryl group,
an alkoxyalkoxyaryl group, an alkenyl group, or an organic group
having an epoxy group, an acryloyl group, a methacryloyl group, a
mercapto group, a sulfonamide group, or a cyano group, or a
combination thereof, and is bonded to a silicon atom through a
Si--C bond, R.sup.8 is an alkoxy group, an acyloxy group, or a
halogen group, and c is an integer of 0 to 3 and a hydrolyzable
silane of Formula (4):
R.sup.9.sub.dSi(R.sup.10).sub.3-d.sub.2Y.sub.e Formula (4) wherein
R.sup.9 is an alkyl group and is bonded to a silicon atom through a
Si--C bond, R.sup.10 is an alkoxy group, an acyloxy group, or a
halogen group, Y is an alkylene group or an arylene group, d is an
integer of 0 or 1, and e is an integer of 0 or 1.
3. The film-forming composition according to claim 1, further
comprising a salt.
4. The film-forming composition according to claim 1, wherein the
film-forming composition is a resist underlayer film-forming
composition for use in a lithography process.
5. A resist underlayer film formed on a semiconductor substrate,
comprising a cured product of the resist underlayer film-forming
composition as claimed in claim 4.
6. A method of producing a semiconductor device comprising: a step
of applying the resist underlayer film-forming composition as
claimed in claim 4 on a semiconductor substrate and baking the
resist underlayer film-forming composition to form a resist
underlayer film; a step of applying a resist composition on the
resist underlayer film to form a resist film; a step of exposing
the resist film; a step of developing the resist film after
exposure to obtain a resist pattern; a step of etching the resist
underlayer film using the resist pattern; and a step of processing
the semiconductor substrate using the patterned resist and the
resist underlayer film.
7. A method of producing a semiconductor device comprising: a step
of forming an organic underlayer film on a semiconductor substrate;
a step of applying the resist underlayer film-forming composition
as claimed in claim 4 on the organic underlayer film and baking the
resist underlayer film-forming composition to form a resist
underlayer film; a step of applying a resist composition on the
resist underlayer film to form a resist film; a step of exposing
the resist film; a step of developing the resist film after
exposure to obtain a resist pattern; a step of etching the resist
underlayer film using the resist pattern; a step of etching the
organic underlayer film using the patterned resist underlayer film;
and a step of processing the semiconductor substrate using the
patterned organic underlayer film.
8. A film-forming composition, the composition comprising: as a
polymer, a hydrolysis-condensation product of a hydrolyzable silane
composed of a combination of: the hydrolyzable silane of Formula
(1): R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4-(a+b) Formula (1)
wherein R.sup.1 is an organic group of Formula (2) and is bonded to
a silicon atom through a Si--C bond or a Si--O bond: ##STR00045##
wherein R.sup.4 is a hydrogen atom, a C.sub.1-10 alkyl group, or an
acyl group, R.sup.5 is a hydrogen atom, a C.sub.1-10 alkyl group,
or a C.sub.1-10 alkyl group having a C.sub.1-10 alkoxy group,
R.sup.6 is a C.sub.1-10 alkyl group, n1 is an integer of 0 to 10,
n2 is an integer of 0 or 1, n3, n4 and n5 are integers, where n3
satisfies 1.ltoreq.n3.ltoreq.5, n4 satisfies 0.ltoreq.n4.ltoreq.4,
and n5 satisfies 0.ltoreq.n5.ltoreq.4, k1 is a bond end with a
silicon atom when n1 is an integer of 1 to 10, k2 is a bond end
with a silicon atom when n1 is 0 and n2 is 1, and k3 is a bond end
with a silicon atom when n1 and n2 are 0; R.sup.2 is an alkyl
group, an aryl group, a halogenated alkyl group, a halogenated aryl
group, an alkoxyaryl group, an alkenyl group, or an organic group
having an epoxy group, an acryloyl group, a methacryloyl group, a
mercapto group, an amino group, or a cyano group, or a combination
thereof, and is bonded to a silicon atom through a Si--C bond;
R.sup.3 is an alkoxy group, an acyloxy group, or a halogen group; a
is an integer of 1; b is an integer of 0 to 2; and a+b is an
integer of 1 to 3; and the hydrolyzable silane of Formula (3):
R.sup.7.sub.cSi(R.sup.8).sub.4-c Formula (3) wherein R.sup.7 is an
alkyl group, an aryl group, a halogenated alkyl group, a
halogenated aryl group, an alkoxyalkyl group, an alkoxyaryl group,
an alkoxyalkoxyaryl group, an alkenyl group, or an organic group
having an epoxy group, an acryloyl group, a methacryloyl group, a
mercapto group, a sulfonamide group, or a cyano group, or a
combination thereof, and is bonded to a silicon atom through a
Si--C bond, R.sup.8 is an alkoxy group, an acyloxy group, or a
halogen group, and c is an integer of 0 to 3.
9. A hydrolyzable silane of Formula (1'):
R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4-(a+b) Formula (1')
wherein R.sup.1 is an organic group of Formula (2') and is bonded
to a silicon atom through a Si--C bond or a Si--O bond:
##STR00046## wherein R.sup.4 is a hydrogen atom, a C.sub.1-10 alkyl
group, or an acyl group, R.sup.5 is a hydrogen atom, a C.sub.1-10
alkyl group, or a C.sub.1-10 alkyl group having a C.sub.1-10 alkoxy
group, R.sup.6 is a C.sub.1-10 alkyl group, n1 is an integer of 0
to 10, n2 is an integer of 0 or 1, wherein n1 and n2 are not 0 at
the same time, n3, n4, and n5 are integers, where n3 satisfies
1.ltoreq.n3.ltoreq.5, n4 satisfies 0.ltoreq.n4.ltoreq.4, and n5
satisfies 0.ltoreq.n5.ltoreq.4, k1 is a bond end with a silicon
atom when n1 is 1 to 10, and k2 is a bond end with a silicon atom
when n1 is 0 and n2 is 1; R.sup.2 is an alkyl group, an aryl group,
a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl
group, an alkenyl group, or an organic group having an epoxy group,
an acryloyl group, a methacryloyl group, a mercapto group, an amino
group, or a cyano group, or a combination thereof, and is bonded to
a silicon atom through a Si--C bond; R.sup.3 is an alkoxy group, an
acyloxy group, or a halogen group; a is an integer of 1; b is an
integer of 0 to 2; and a+b is an integer of 1 to 3.
Description
TECHNICAL FIELD
The present invention relates to a film-forming composition
including a hydrolyzable silane having a cross-linking reactive
group.
BACKGROUND ART
A variety of materials are used in the form of films, coatings, and
coats. Among these materials, for example, siloxane materials are
used for improving heat resistance, transparency, plasma
resistance, planarization property, and the like. In these
materials, the technique of siloxane cross-linking by dehydration
and condensation of silanol is generally adopted. Another method
for causing cross-linking is introducing acrylate groups into a
silicone polymer (see Patent Document 1). It is shown that these
groups can be cross-linked and cured by radiation of UV light.
Organosiloxane using methylol cross-linking is also proposed (see
Patent Document 2).
More specifically, it is proposed to cross-link an
organopolysiloxane using a composition including at least two
organopolysiloxane units and a nitrogen-containing compound having
methylol group.
It is also proposed to use a composition having a cross-linking
material using methylol cross-linking as a resist underlayer for
use in the lithography process for semiconductor devices (see
Patent Document 3).
PRIOR ART DOCUMENTS
Patent Documents
Patent Document 1: Japanese Patent Application Publication No.
H3-275769 (JP H3-275769 A)
Patent Document 2: Japanese Patent Application Publication No.
2009-537645 (JP 2009-537645 A)
Patent Document 3: Japanese Patent Application Publication No.
2011-170059 (JP 2011-170059 A)
SUMMARY OF THE INVENTION
Problem to be Solved by the Invention
In conventional polysiloxanes having cross-linkability, a
cross-linking reaction occurs between the functional group built in
the side chain of a polysiloxane, for example, the functional group
such as carboxy group, hydroxy group, and epoxy group, and a
cross-linkable compound.
In these cross-linking systems, a low-molecular cross-linking agent
is involved in a cross-linking reaction, and cross-linking failures
often occur.
The present invention is aimed to provide a composition that forms
a sufficiently strong cross-linked structure and is highly
resistant against chemicals, by introducing alkoxymethylphenyl
group causing a cross-linking reaction to the side chain of a
polysiloxane to allow the cross-linking group to mutually form a
cross-linked structure or form a cross-linked structure with
another component.
Means for Solving the Problem
The present invention provides:
according to a first aspect, a film-forming composition comprising,
as a silane, a hydrolyzable silane, a hydrolysis product thereof,
or a hydrolysis-condensation product thereof, in which the
hydrolyzable silane includes a hydrolyzable silane of Formula (1):
R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4-(a+b) Formula (1)
[in Formula (1), R.sup.1 is an organic group of Formula (2) and is
bonded to a silicon atom through a Si--C bond or a Si--O bond:
##STR00002##
(in Formula (2), R.sup.4 is a hydrogen atom, a C.sub.1-10 alkyl
group, or an acyl group, R.sup.5 is a hydrogen atom, a C.sub.1-10
alkyl group, or a C.sub.1-10 alkyl group having a C.sub.1-10 alkoxy
group, R.sup.6 is a C.sub.1-10 alkyl group, n1 is an integer of 0
to 10, n2 is an integer of 0 or 1, n3, n4 and n5 are integers,
where n3 satisfies 1.ltoreq.n3.ltoreq.5, n4 satisfies
0.ltoreq.n4.ltoreq.4, and n5 satisfies 0.ltoreq.n5.ltoreq.4, k1 is
a bond end with a silicon atom when n1 is 1 to 10, k2 is a bond end
with a silicon atom when n1 is 0 and n2 is 1, and k3 is a bond end
with a silicon atom when n1 and n2 are 0); R.sup.2 is an alkyl
group, an aryl group, a halogenated alkyl group, a halogenated aryl
group, an alkoxyaryl group, an alkenyl group, or an organic group
having an epoxy group, an acryloyl group, a methacryloyl group, a
mercapto group, an amino group, or a cyano group, or a combination
thereof, and is bonded to a silicon atom through a Si--C bond;
R.sup.3 is an alkoxy group, an acyloxy group, or a halogen group; a
is an integer of 1; b is an integer of 0 to 2; and a+b is an
integer of 1 to 3];
according to a second aspect, the film-forming composition
according to the first aspect, in which the hydrolyzable silane is
a combination of the hydrolyzable silane of Formula (1) with
another hydrolyzable silane, in which the other hydrolyzable silane
is at least one hydrolyzable silane selected from the group
consisting of a hydrolyzable silane of Formula (3):
R.sup.7.sub.cSi(R.sup.8).sub.4-c Formula (3)
(in Formula (3), R.sup.7 is an alkyl group, an aryl group, a
halogenated alkyl group, a halogenated aryl group, an alkoxyalkyl
group, an alkoxyaryl group, an alkoxyalkoxyaryl group, an alkenyl
group, or an organic group having an epoxy group, an acryloyl
group, a methacryloyl group, a mercapto group, a sulfonamide group,
or a cyano group, or a combination thereof, and is bonded to a
silicon atom through a Si--C bond, R.sup.8 is an alkoxy group, an
acyloxy group, or a halogen group, and c is an integer of 0 to 3),
and a hydrolyzable silane of Formula (4):
R.sup.9.sub.dSi(R.sup.10).sub.3-d.sub.2Y.sub.e Formula (4)
(in Formula (4), R.sup.9 is an alkyl group and is bonded to a
silicon atom through a Si--C bond, R.sup.10 is an alkoxy group, an
acyloxy group, or a halogen group, Y is an alkylene group or an
arylene group, d is an integer of 0 or 1, and e is an integer of 0
or 1);
according to a third aspect, a film-forming composition comprising,
as a polymer, a hydrolysis-condensation product of a hydrolyzable
silane composed of a combination of the hydrolyzable silane of
Formula (1) in the first aspect and the hydrolyzable silane of
Formula (3) in the second aspect;
according to a fourth aspect, the film-forming composition
according to any one of the first aspect to the third aspect,
further comprising a salt;
according to a fifth aspect, the film-forming composition according
to any one of the first aspect to the fourth aspect, in which the
film-forming composition is a resist underlayer film-forming
composition for use in a lithography process;
according to a sixth aspect, a resist underlayer film formed on a
semiconductor substrate, comprising a cured product of the resist
underlayer film-forming composition in the fifth aspect;
according to a seventh aspect, a method of producing a
semiconductor device comprising the steps of: applying the resist
underlayer film-forming composition in the fifth aspect on a
semiconductor substrate and baking the resist underlayer
film-forming composition to form a resist underlayer film; applying
a resist composition on the resist underlayer film to form a resist
film; exposing the resist film; developing the resist film after
exposure to obtain a resist pattern; etching the resist underlayer
film using the resist pattern; and processing the semiconductor
substrate using the patterned resist and resist underlayer
film;
according to an eighth aspect, a method of producing a
semiconductor device comprising the steps of: forming an organic
underlayer film on a semiconductor substrate; applying the resist
underlayer film-forming composition in the fifth aspect on the
organic underlayer film and baking the resist underlayer
film-forming composition to form a resist underlayer film; applying
a resist composition on the resist underlayer film to form a resist
film; exposing the resist film; developing the resist film after
exposure to obtain a resist pattern; etching the resist underlayer
film using the resist pattern; etching the organic underlayer film
using the patterned resist underlayer film; and processing the
semiconductor substrate using the patterned organic underlayer
film; and
according to a ninth aspect, a hydrolyzable silane of Formula (1'):
R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4-(a+b) Formula (1') [in
Formula (1'), R.sup.1 is an organic group of Formula (2') and is
bonded to a silicon atom through a Si--C bond or a Si--O bond:
##STR00003##
(in Formula (2'), R.sup.4 is a hydrogen atom, a C.sub.1-10 alkyl
group, or an acyl group, R.sup.5 is a hydrogen atom, a C.sub.1-10
alkyl group, or a C.sub.1-10 alkyl group having a C.sub.1-10 alkoxy
group, R.sup.6 is a C.sub.1-10 alkyl group, n1 is an integer of 0
to 10, n2 is an integer of 0 or 1, n3, n4, and n5 are integers,
where n3 satisfies 1.ltoreq.n3.ltoreq.5, n4 satisfies
0.ltoreq.n4.ltoreq.4, and n5 satisfies 0.ltoreq.n5.ltoreq.4, k1 is
a bond end with a silicon atom when n1 is 1 to 10, k2 is a bond end
with a silicon atom when n1 is 0 and n2 is 1, and k3 is a bond end
with a silicon atom when n1 and n2 are 0); R.sup.2 is an alkyl
group, an aryl group, a halogenated alkyl group, a halogenated aryl
group, an alkoxyaryl group, an alkenyl group, or an organic group
having an epoxy group, an acryloyl group, a methacryloyl group, a
mercapto group, an amino group, or a cyano group, or a combination
thereof, and is bonded to a silicon atom through a Si--C bond;
R.sup.3 is an alkoxy group, an acyloxy group, or a halogen group; a
is an integer of 1; b is an integer of 0 to 2; and a+b is an
integer of 1 to 3].
Effects of the Invention
In the present invention, in the silane component,
alkoxymethylphenyl group or the like causing a cross-linking
reaction is introduced to the side chain of a polysiloxane to allow
this cross-linking group to mutually form a cross-linking reaction
with electron-rich phenyl group. This alkoxymethylphenyl group can
form a cross-linked structure also with another hydroxy group and
can form a sufficiently strong cross-linked structure. Therefore,
the film formed after curing the composition of the present
invention is excellent mechanically as well as in resistance
against chemicals.
The film-forming composition of the present invention can form such
excellent films and therefore can be used as a film-forming
composition for various applications. An example of the usage is a
resist underlayer film-forming composition for forming a resist
underlayer film for use in a multilayer process in semiconductor
lithography using the etching resistance that siloxane
intrinsically has. Typically, the resist is thinned in order to
prevent pattern collapse involved with scaling-down of patterns. In
doing so, using that the etching rate ratio of the siloxane layer
and the organic layer is changed by combining etching gasses, the
process is performed such that a resist pattern is transferred to
the underlying silicon hard mask and further transferred to the
underlying organic underlayer film, and finally the silicon
substrate is processed. The film-forming composition of the present
invention can also be used as a composition for forming the silicon
hard mask (resist underlayer film) used in this process.
The film-forming composition of the present invention is a
silicone-based composition and can be used as a hole-filling
material for the substrate required to have planarization property,
by controlling the degree of curing by controlling the temperatures
at which a cross-linking reaction is caused by alkoxymethylphenyl
group. Since the fluidity of the film-forming composition of the
present invention is kept in a temperature range lower than the
temperature at which a cross-linking reaction by alkoxymethylphenyl
group occurs, first, minute holes on the substrate are filled with
the composition kept at a temperature lower than the temperature
causing a cross-linking reaction, and then the temperature is
increased to cause a cross-linking reaction, whereby a highly
planarized film can be formed with minute holes filled
sufficiently.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of an uneven substrate used in a
hole-filling evaluation test.
MODES FOR CARRYING OUT THE INVENTION
The present invention provides a film-forming composition
including, as a silane, a hydrolyzable silane, a hydrolysis product
thereof, or a hydrolysis-condensation product thereof. The
hydrolyzable silane includes a hydrolyzable silane of Formula
(1).
The film-forming composition of the present invention includes the
hydrolyzable silane of Formula (1), a hydrolysis product thereof,
or a hydrolysis-condensation product thereof, and a solvent. The
film-forming composition of the present invention may optionally
include an acid, water, an alcohol, a curing catalyst, an acid
generator, another organic polymer, a light-absorptive compound, a
surfactant, and the like.
The solid content in the film-forming composition of the present
invention is, for example, 0.1 to 50% by mass, or 0.1 to 30% by
mass, 0.1 to 25% by mass. As used herein, the solid content refers
to the content obtained by removing the solvent component from all
the components of the film-forming composition.
The proportion of the hydrolyzable silane, the hydrolysis product
thereof, and the hydrolysis-condensation product thereof in the
solid content is 20% by mass or more, for example, 50 to 100% by
mass, 60 to 99%/by mass, 70 to 99% by mass.
The hydrolyzable silane, the hydrolysis product thereof, and the
hydrolysis-condensation product thereof can be used in the form of
a mixture thereof. The condensation product obtained by hydrolyzing
a hydrolyzable silane and condensing the resultant hydrolysis
product may be used. When a hydrolysis-condensation product is
obtained, a partial hydrolysis product in which hydrolysis is not
completed or a mixture including a silane compound mixed with the
hydrolysis-condensation product may be used. This condensation
product is a polymer having a polysiloxane structure. This
polysiloxane includes the hydrolyzable silane of Formula (1), or a
hydrolysis-condensation product of the hydrolyzable silane of
Formula (1) and another hydrolyzable silane (for example, the
hydrolyzable silane of Formula (3)). Alternatively, the
hydrolyzable silane of Formula (1), or a hydrolyzable silane
composed of a mixture of the hydrolyzable silane of Formula (1) and
the hydrolyzable silane of Formula (3) can be added to the
hydrolyzable silane of Formula (1), or a hydrolysis-condensation
product (polysiloxane) of a hydrolysis product of a hydrolyzable
silane composed of a combination of the hydrolyzable silane of
Formula (1) and the hydrolyzable silane of Formula (3).
In Formula (1), R.sup.1 is an organic group of Formula (2) and is
bonded to a silicon atom through a Si--C bond or a Si--O bond.
R.sup.2 is an alkyl group, an aryl group, a halogenated alkyl
group, a halogenated aryl group, an alkoxyaryl group, an alkenyl
group, or an organic group having an epoxy group, an acryloyl
group, a methacryloyl group, a mercapto group, an amino group, or a
cyano group, or a combination thereof, and is bonded to a silicon
atom through a Si--C bond. R.sup.3 is an alkoxy group, an acyloxy
group, or a halogen group. Then, a is an integer of 1, b is an
integer of 0 to 2, and a+b is an integer of 1 to 3.
In Formula (2), R.sup.4 is a hydrogen atom, a C.sub.1-10 alkyl
group, or an acyl group, R.sup.5 is a hydrogen atom, a C.sub.1-10
alkyl group, or a C.sub.1-10 alkyl group having a C.sub.1-10 alkoxy
group, R.sup.6 is a C.sub.1-10 alkyl group, n1 is an integer of 0
to 10, n2 is an integer of 0 or 1, n3, n4, and n5 are integers,
where n3 satisfies 1.ltoreq.n3.ltoreq.5, n4 satisfies
0.ltoreq.n4.ltoreq.4, and n5 satisfies 0.ltoreq.n5.ltoreq.4. The k1
portion, the k2 portion, or the k3 portion is a bond end with a
silicon atom, k1 is a bond end with a silicon atom when n1 is 1 to
10, k2 is a bond end with a silicon atom when n1 is 0 and n2 is 1,
and k3 is a bond end with a silicon atom when n1 and n2 are 0. In
the k1 portion, the one bonded to a silicon atom can be
selected.
The alkyl group is, for example, a C.sub.1-10 alkyl group, and
examples thereof include methyl group, ethyl group, n-propyl group,
i-propyl group, cyclopropyl group, n-butyl group, i-butyl group,
s-butyl group, t-butyl group, cyclobutyl group,
1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl
group, 1-methyl-n-butyl group, 2-methyl-n-butyl group,
3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group,
1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group,
1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl
group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group,
1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group,
1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl
group, l-methyl-n-pentyl group, 2-methyl-n-pentyl group,
3-methyl-n-pentyl group, 4-methyl-n-pentyl group,
1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group,
1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group,
2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group,
1-ethyl-n-butyl group, 2-ethyl-n-butyl group,
1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group,
1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group,
cyclohexyl group, I-methyl-cyclopentyl group, 2-methyl-cyclopentyl
group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group,
2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group,
1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group,
2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group,
2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group,
1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group,
1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group,
1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl
group, 2,2,3-trimethyl-cyclopropyl group,
1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl
group, 2-ethyl-2-methyl-cyclopropyl group, and
2-ethyl-3-methyl-cyclopropyl group.
The aryl group is, for example, a C.sub.6-40 aryl group, and
examples thereof include phenyl group, o-methylphenyl group,
m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group,
m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group,
p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group,
p-nitrophenyl group, p-cyanophenyl group, a-naphthyl group,
.beta.-naphthyl group, o-biphenylyl group, m-biphenylyl group,
p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl
group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl
group, 4-phenanthryl group, and 9-phenanthryl group.
The alkenyl group is, for example, a C.sub.2-10 alkenyl group, and
examples thereof include ethenyl group, 1-propenyl group,
2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group,
2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group,
2-methyl-2-propenyl group, 1-ethylethenyl group,
1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl
group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group,
1-n-propylethenyl group, 1-methyl-1-butenyl group,
1-methyl-2-butenyl group, 1-methyl-3-butenyl group,
2-ethyl-2-propenyl group, 2-methyl-1-butenyl group,
2-methyl-2-butenyl group, 2-methyl-3-butenyl group,
3-methyl-1-butenyl group, 3-methyl-2-butenyl group,
3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group,
1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group,
1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group,
2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group,
2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group,
1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group,
1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group,
1-n-butylethenyl group, 2-methyl-1-pentenyl group,
2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group,
2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group,
3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group,
3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group,
3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group,
4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group,
4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group,
1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group,
1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group,
1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group,
1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group,
1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group,
2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group,
2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group,
2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group,
1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl
group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group,
2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl
group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group,
1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl
group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl
group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group,
1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group,
2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group,
2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group,
2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group,
3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group,
3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group,
3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl
group, and 3-cyclohexenyl group.
The acyl group is, for example, a C.sub.2-10 acyl group, and
examples thereof include methylcarbonyl group, ethylcarbonyl group,
n-propylcarbonyl group, i-propylcarbonyl group, cyclopropylcarbonyl
group, n-butylcarbonyl group, i-butylcarbonyl group,
s-butylcarbonyl group, t-butylcarbonyl group, cyclobutylcarbonyl
group, 1-methyl-cyclopropylcarbonyl group,
2-methyl-cyclopropylcarbonyl group, n-pentylcarbonyl group,
1-methyl-n-butylcarbonyl group, 2-methyl-n-butylcarbonyl group,
3-methyl-n-butylcarbonyl group, 1,1-dimethyl-n-propylcarbonyl
group, 1,2-dimethyl-n-propylcarbonyl group,
2,2-dimethyl-n-propylcarbonyl group, 1-ethyl-n-propylcarbonyl
group, cyclopentylcarbonyl group, 1-methyl-cyclobutylcarbonyl
group, 2-methyl-cyclobutylcarbonyl group,
3-methyl-cyclobutylcarbonyl group, 1,2-dimethyl-cyclopropylcarbonyl
group, 2,3-dimethyl-cyclopropylcarbonyl group,
1-ethyl-cyclopropylcarbonyl group, 2-ethyl-cyclopropylcarbonyl
group, n-hexylcarbonyl group, 1-methyl-n-pentylcarbonyl group,
2-methyl-n-pentylcarbonyl group, 3-methyl-n-pentylcarbonyl group,
4-methyl-n-pentylcarbonyl group, 1,1-dimethyl-n-butylcarbonyl
group, 1,2-dimethyl-n-butylcarbonyl group,
1,3-dimethyl-n-butylcarbonyl group, 2,2-dimethyl-n-butylcarbonyl
group, 2,3-dimethyl-n-butylcarbonyl group,
3,3-dimethyl-n-butylcarbonyl group, 1-ethyl-n-butylcarbonyl group,
2-ethyl-n-butylcarbonyl group, and 1,1,2-trimethyl-n-propylcarbonyl
group.
Examples of the organic group having an epoxy group include
glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl,
and epoxycyclohexyl.
Examples of the organic group having an acryloyl group include
acryloylmethyl, acryloylethyl, and acryloylpropyl.
Examples of the organic group having a methacryloyl group include
methacryloylmethyl, methacryloylethyl, and methacryloylpropyl.
Examples of the organic group having a mercapto group include
ethylmercapto, butylmercapto, hexylmercapto, and octylmercapto.
Examples of the organic group having an amino group include amino
group, aminomethyl group, and aminoethyl group.
Examples of the organic group having a cyano group include
cyanoethyl and cyanopropyl.
Examples of the C.sub.1-20 or C.sub.1-10 alkoxy group include
alkoxy groups having a linear, branched, or cyclic alkyl moiety
having a carbon atom number of 1 to 20, such as methoxy group,
ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group,
i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group,
1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy
group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group,
2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy
group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group,
3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group,
1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group,
1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group,
2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group,
1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group,
1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group,
1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy
group. Examples of the cyclic alkoxy group include cyclopropoxy
group, cyclobutoxy group, 1-methyl-cyclopropoxy group,
2-methyl-cyclopropoxy group, cyclopentyloxy group,
1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group,
3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group,
2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group,
2-ethyl-cyclopropoxy group, cyclohexyloxy group,
1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group,
3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group,
2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group,
1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group,
2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group,
2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group,
1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group,
1-i-propyl-cyclopropoxy group, 2-i-propyl-cyclopropoxy group,
1,2,2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy
group, 2,2,3-trimethyl-cyclopropoxy group,
1-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-1-methyl-cyclopropoxy
group, 2-ethyl-2-methyl-cyclopropoxy group, and
2-ethyl-3-methyl-cyclopropoxy group.
Examples of the C.sub.2-20, C.sub.1-10 acyloxy group include
methylcarbonyloxy group, ethylcarbonyloxy group,
n-propylcarbonyloxy group, i-propylcarbonyloxy group,
n-butylcarbonyloxy group, i-butylcarbonyloxy group,
s-butylcarbonyloxy group, t-butylcarbonyloxy group,
n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group,
2-methyl-n-butylcarbonyloxy group, 3-methyl-n-butylcarbonyloxy
group, 1,1-dimethyl-n-propylcarbonyloxy group,
1,2-dimethyl-n-propylcarbonyloxy group,
2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl-n-propylcarbonyloxy
group, n-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy
group, 2-methyl-n-pentylcarbonyloxy group,
3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy
group, 1,1-dimethyl-n-butylcarbonyloxy group,
1,2-dimethyl-n-butylcarbonyloxy group,
1,3-dimethyl-n-butylcarbonyloxy group,
2,2-dimethyl-n-butylcarbonyloxy group,
2,3-dimethyl-n-butylcarbonyloxy group,
3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy
group, 2-ethyl-n-butylcarbonyloxy group,
1,1,2-trimethyl-n-propylcarbonyloxy group,
1,2,2-trimethyl-n-propylcarbonyloxy group,
1-ethyl-1-methyl-n-propylcarbonyloxy group,
1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy
group, and tosylcarbonyloxy group.
Examples of the halogen group include fluorine, chlorine, bromine,
and iodine.
The hydrolyzable silane can be used as a combination of the
hydrolyzable silane of Formula (1) and another hydrolyzable
silane.
As another hydrolyzable silane, at least one hydrolyzable silane
selected from the group consisting of Formula (3) and Formula (4)
can be used.
In Formula (3), R.sup.7 is an alkyl group, an aryl group, a
halogenated alkyl group, a halogenated aryl group, an alkoxyalkyl
group, an alkoxyaryl group, an alkoxyalkoxyaryl group, an alkenyl
group, or an organic group having an epoxy group, an acryloyl
group, a methacryloyl group, a mercapto group, a sulfonamide group,
or a cyano group, or a combination thereof, and is bonded to a
silicon atom through a Si--C bond, R.sup.8 is an alkoxy group, an
acyloxy group, or a halogen group, and c is an integer of 0 to
3.
In Formula (4), R.sup.9 is an alkyl group and is bonded to a
silicon atom through a Si--C bond, R.sup.10 is an alkoxy group, an
acyloxy group, or a halogen group, Y is an alkylene group or an
arylene group, d is an integer of 0 or 1, and e is an integer of 0
or 1.
Those illustrated above can be used as the alkyl group, the aryl
group, the halogenated alkyl group, the halogenated aryl group, the
alkoxyalkyl group, the alkoxyaryl group, the alkoxyalkoxyaryl
group, the alkenyl group, or the organic group having an epoxy
group, an acryloyl group, a methacryloyl group, a mercapto group, a
sulfonamide group, or a cyano group, the alkoxy group, the acyloxy
group, and the halogen group.
The alkoxyalkyl group is an alkyl group in which alkoxy group is
substituted, and examples thereof include methoxymethyl group,
ethoxymethyl group, ethoxyethyl group, and ethoxymethyl group.
The alkoxyaryl group is an aryl group in which alkoxy group is
substituted, and examples thereof include methoxyphenyl group and
ethoxyphenyl group.
The alkoxyalkoxyaryl group is an aryl group in which the organic
group in which alkoxy group is substituted with alkoxy group is
substituted, and examples thereof include methoxymethoxyphenyl
group, methoxyethoxyphenyl group, ethoxymethoxyphenyl group, and
ethoxyethoxyphenyl group.
The film-forming composition can include, as a polymer, a
hydrolysis-condensation product of a hydrolyzable silane composed
of a combination of the hydrolyzable silane of Formula (1) and the
hydrolyzable silane of Formula (3).
Examples of the hydrolyzable silane of Formula (1) are illustrated
below.
##STR00004## ##STR00005##
In the formulae above, Me is a methyl group and Et is an ethyl
group. In the following description, these abbreviations may be
used.
In the present invention, the hydrolyzable silane is a combination
of the hydrolyzable silane of Formula (1) and another hydrolyzable
silane. At least one hydrolyzable silane selected from the group
consisting of Formula (3) and Formula (4) can be used as another
hydrolyzable silane.
Examples of the silicon-containing compound of Formula (3) include
tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane,
tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane,
tetra-n-butoxysilane, methyltrimethoxysilane,
methyltrichlorosilane, methyltriacetoxysilane,
methyltripropoxysilane, methyltributoxysilane,
methyltriamyloxysilane, methyltriphenoxysilane,
tnethyltribenzyloxysilane, methyltriphenethyloxysilane,
glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane,
.alpha.-glycidoxyethyltrimethoxysilane,
.alpha.-glycidoxyethyltriethoxysilane,
.beta.-glycidoxyethyltrimethoxysilane,
.beta.-gycidoxyethyltriethoxysilane,
.alpha.-glycidoxypropyltrimethoxysilane,
.alpha.-glycidoxypropyltriethoxysilane,
.beta.-glycidoxypropyltrimethoxysilane,
.beta.-glycidoxypropyltriethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-glycidoxypropyltriethoxysilane,
.gamma.-glycidoxypropyltripropoxysilane,
.gamma.-glycidoxypropyltributoxysilane,
.gamma.-glycidoxypropyltriphenoxysilane,
.alpha.-glycidoxybutyltriniethoxysilane,
.alpha.-glycidoxybutyltriethoxysilane,
.beta.-glycidoxybutyltriethoxysilane,
.gamma.-glycidoxybutyltrimethoxysilane,
.gamma.-glycidoxybutyltriethoxysilane,
.delta.-glycidoxybutyltrimethoxysilane,
.delta.-glycidoxybutyltriethoxysilane,
(3,4-epoxycyclohexyl)methyltrimethoxysilane,
(3,4-epoxycyclohexyl)methyltriethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltriethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltripropoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltributoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltriphenoxysilane,
.gamma.-(3,4-epoxycyclohexyl)propyltrimethoxysilane,
.gamma.-(3,4-epoxycyclohexyl)propyltriethoxysilane,
.delta.-(3,4-epoxycyclohexyl)butyltrimethoxysilane,
.delta.-(3,4-epoxycyclohexyl)butyltriethoxysilane,
glycidoxymethylmethyldimethoxysilane,
glycidoxymethylmethyldiethoxysilane,
.alpha.-glycidoxyethylmethyldimethoxysilane.
.alpha.-glycidoxyethylmethyldiethoxysilane,
.beta.-glycidoxyethylmethyldimethoxysilane,
.beta.-glycidoxyethylethyldimethoxysilane.
.alpha.-glycidoxypropylmethyldimethoxysilane,
.alpha.-glycidoxypropylmethyldiethoxysilane,
.beta.-glycidoxypropylmethyldimethoxysilane,
.beta.-glycidoxypropylethyldimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-glycidoxypropyimethyldiethoxysilane,
.gamma.-glycidoxypropylmethyldipropoxysilane,
.gamma.-glycidoxypropylmethyldibutoxysilane,
.gamma.-glycidoxypropylmethyldiphenoxysilane,
.gamma.-glycidoxypropylethyldimethoxysilane,
.gamma.-glycidoxypropylethyldiethoxysilane,
.gamma.-glycidoxypropylvinyldimethoxysilane,
.gamma.-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane,
ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane,
vinyltriacetoxysilane, vinyltriethoxysilane,
methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane,
methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane,
methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane,
miethoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane,
inethoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane,
methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane,
ethoxyphenyltriinethoxysilane, ethoxyphenyltriethoxysilane,
ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane,
ethoxybenzyltrimethoxysilane, ethoxybenziltriethoxysilane,
ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane,
isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane,
isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane,
isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane,
isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane,
t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane,
t-butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane,
t-butoxybenzyltrirnethi xysilanc, t-butoxybenzyltriethoxysilane,
t-butoxybenzyltriacetoxysilane, t-butoxybenzyltrichlorosilane,
methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane,
methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane,
ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane,
ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane,
.gamma.-chloropropyltritnethoxysilane,
.gamma.-chloropropyltriethoxysilane,
.gamma.-chloropropyltriacetoxysilane,
3,3,3-trifluoropropyltrimethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane,
.gamma.-mercaptopropyltriethoxysilane,
.beta.-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane,
chloromethyltriethoxysilane, dimethyldimethoxysilane,
phenylmethyldimethoxysilane, dimethyldiethoxysilane,
phenylmethyldiethoxysilane,
.gamma.-chloropropylmethyldimethoxysilane,
.gamma.-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane,
.gamma.-methacryloxypropylmethyldimethoxysilane,
.gamma.-methacryloxypropylmethyldiethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
.gamma.-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane,
and methylvinyldiethoxysilane.
The hydrolyzable silanes below may be used.
##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010##
##STR00011## ##STR00012## ##STR00013##
Examples of the silicon-containing compound of Formula (4) include
methylenebistrimethoxysilane, methylenebistrichlorosilane,
methylenebistriacetoxysilane, ethylenebistriethoxysilane,
ethylenebistrichlorosilane, ethylenebistriacetoxysilane,
propylenebistriethoxysilane, butylenebistrimethoxysilane,
phenylenebistrimethoxysilane, phenylenebistriethoxysilane,
phenylenebismethyldiethoxysilane,
phenylenebismethyldimethoxysilane, naphthylenebistrimethoxysilane,
bistrimethoxydisilane, bistriethoxydisilane,
bisethyldiethoxydisilane, and bismethyldimethoxydisilane.
In the present invention, silanes having sulfone group or silanes
having sulfonamide group may further be used as the hydrolyzable
silane, and examples thereof can be illustrated below.
##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018##
##STR00019##
Specific examples of the hydrolysis-condensation product
(polysiloxane) used in the present invention are illustrated
below.
##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024##
##STR00025##
The hydrolysis-condensation product (polyorganosiloxane) of the
hydrolyzable silane above is the condensation product having a
weight average molecular weight of 1000 to 1000000, or 1000 to
100000. These molecular weights are molecular weights obtained in
terms of polystyrene through GPC analysis.
The measurement conditions of GPC may include, for example, a GPC
apparatus (trade name: HLC-8220GPC, manufactured by TOSOH
CORPORATION), a GPC column (trade name: Shodex KF803L, KF802,
KF801, manufactured by SHOWA DENKO K.K.), column temperature of
40.degree. C., eluent (elution solvent) of tetrahydrofuran, flow
rate (flow velocity) of 1.0 ml/min, and a standard sample of
polystyrene (manufactured by SHOWA DENKO) K.K.).
In the hydrolysis of alkoxysilyl group, acyloxysilyl group, or
halogenated silyl group, 0.5 to 100 moles, preferably, 1 to 10
moles of water is used per 1 mole of the hydrolyzable group.
Furthermore, 0.001 to 10 moles, preferably 0.001 to 1 mole of a
hydrolysis catalyst can be used per 1 mole of the hydrolyzable
group.
The reaction temperature in hydrolysis and condensation is usually
20 to 80.degree. C.
The hydrolysis may be performed completely or may be performed
partially. That is, a hydrolysis product or a monomer may be left
in the hydrolysis-condensation product.
A catalyst may be used during hydrolysis and condensation.
Examples of the hydrolysis catalyst include metal chelate
compounds, organic acids, inorganic acids, organic bases, and
inorganic bases.
Examples of the metal chelate compound serving as a hydrolysis
catalyst include titanium chelate compounds such as:
triethoxy-mono(acetylacetonate)titanium,
tri-n-propoxy-mono(acetylacetonate)titanium,
tri-i-propoxy-mono(acetylacetonate)titanium,
tri-n-butoxy-mono(acetylacetonate)titanium,
tri-sec-butoxy-mono(acetylacetonate)titanium,
tri-t-butoxy-mono(acetylacetonate)titanium,
diethoxy-bis(acetylacetonate)titanium,
di-n-propoxy-bis(acetylacetonate)titanium,
di-i-propoxy-bis(acetylacetonate)titanium,
di-n-butoxy-bis(acetylacetonate)titanium,
di-sec-butoxy-bis(acetylacetonate)titanium,
di-t-butoxy-bis(acetylacetonate)titanium,
monoethoxy-tris(acetylacetonate)titanium,
mono-n-propoxy-tris(acetylacetonate)titanium,
mono-i-propoxy-tris(acetylacetonate)titanium,
mono-n-butoxy-tris(acetylacetonate)titanium,
mono-sec-butoxy-tris(acetylacetonate)titanium,
mono-t-butoxy-tris(acetylacetonate)titanium,
tetrakis(acetylacetonate)titanium,
triethoxy-mono(ethylacetoacetate)titanium,
tri-n-propoxy-mono(ethylacetoacetate)titanium,
tri-i-propoxy-mono(ethylacetoacetate)titanium,
tri-n-butoxy-mono(ethylacetoacetate)titanium,
tri-sec-butoxy-mono(ethylacetoacetate)titanium,
tri-t-butoxy-mono(ethylacetoacetate)titanium,
diethoxy-bis(ethylacetoacetate)titanium,
di-n-propoxy-bis(ethylacetoacetate)titanium,
di-1-propoxy-bis(ethylacetoacetate)titanium,
di-n-butoxy-bis(ethylacetoacetate)titanium,
di-sec-butoxy-bis(ethylacetoacetate)titanium,
di-t-butoxy-bis(ethylacetoacetate)titanium,
monoethoxy-tris(ethylacetoacetate)titanium,
mono-n-propoxy-tris(ethylacetoacetate)titanium,
mono-1-propoxy-tris(ethylacetoacetate)titanium,
mono-n-butoxy-tris(ethylacetoacetate)titanium,
mono-sec-butoxy-tris(ethylacetoacetate)titanium,
mono-t-butoxy-tris(ethylacetoacetate)titanium,
tetrakis(ethylacetoacetate)titanium,
mono(acetylacetonate)tris(ethylacetoacetate)titanium,
bis(acetylacetonate)bis(ethylacetoacetate)titanium, and
tris(acetylacetonate)mono(ethylacetoacetate)titanium; zirconium
chelate compounds such as:
triethoxy-mono(acetylacetonate)zirconium,
tri-n-propoxy-mono(acetylacetonate)zirconium,
tri-i-propoxy-mono(acetylacetonate)zirconium,
tri-n-butoxy-mono(acetylacetonate)zirconium,
tri-sec-butoxy-mono(acetylacetonate)zirconium,
tri-t-butoxy-mono(acetylacetonate)zirconium,
diethoxy-bis(acetylacetonate)zirconium,
di-n-propoxy-bis(acetylacetonate)zirconium,
di-i-propoxy-bis(acetylacetonate)zirconium,
di-n-butoxy-bis(acetylacetonate)zirconium,
di-sec-butoxy-bis(acetylacetonate)zirconium,
di-t-butoxy-bis(acetylacetonate)zirconium,
monoethoxy-tris(acetylacetonate)zirconium,
mono-n-propoxy-tris(acetylacetonate)zirconium,
mono-i-propoxy-tris(acetylacetonate)zirconium,
mono-n-butoxy-tris(acetylacetonate)zirconium,
mono-sec-butoxy-tris(acetylacetonate)zirconium,
mono-t-butoxy-tris(acetylacetonate)zirconium,
tetrakis(acetylacetonate)zirconium,
triethoxy-mono(ethylacetoacetate)zirconium,
tri-n-propoxy-mono(ethylacetoacetate)zirconium,
tri-i-propoxy-mono(ethylacetoacetate)zirconium,
tri-n-butoxy-mono(ethylacetoacetate)zirconium,
tri-sec-butoxy-mono(ethylacetoacetate)zirconium,
tri-t-butoxy-mono(ethylacetoacetate)zirconium,
diethoxy-bis(ethylacetoacetate)zirconium,
di-n-propoxy-bis(ethylacetoacetate)zirconium,
di-i-propoxy-bis(ethylacetoacetate)zirconium,
di-n-butoxy-bis(ethylacetoacetate)zirconium,
di-sec-butoxy-bis(ethylacetoacetate)zirconium,
di-t-butoxy-bis(ethylacetoacetate)zirconium,
monoethoxy-tris(ethylacetoacetate)zirconium,
mono-n-propoxy-tris(ethylacetoacetate)zirconium,
mono-i-propoxy-tris(ethylacetoacetate)zirconium,
mono-n-butoxy-tris(ethylacetoacetate)zirconium,
mono-sec-butoxy-tris(ethylacetoacetate)zirconium,
mono-t-butoxy-tris(ethylacetoacetate)zirconium,
tetrakis(ethylacetoacetate)zirconium,
mono(acetylacetonate)tris(ethylacetoacetate)zirconium,
bis(acetylacetonate)bis(ethylacetoacetate)zirconium, and
tris(acetylacetonate)mono(ethylacetoacetate)zirconium; and
aluminum chelate compounds such as:
tris(acetylacetonate)aluminum and
tris(ethylacetoacetate)aluminum.
Examples of the organic acid serving as a hydrolysis catalyst
include acetic acid, propionic acid, butanoic acid, pentanoic acid,
hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid,
decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic
acid, sebacic acid, gallic acid, butyric acid, mellitic acid,
arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid,
linolic acid, linoleic acid, salicylic acid, benzoic acid,
p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid,
monochloroacetic acid, dichloroacetic acid, trichloroacetic acid,
trifloroacetic acid, formic acid, malonic acid, sulfonic acids,
phthalic acid, fumaric acid, citric acid, and tartaric acid.
Examples of the inorganic acid serving as a hydrolysis catalyst
include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric
acid, and phosphoric acid.
Examples of the organic base serving as a hydrolysis catalyst
include pyridine, pyrrole, piperazine, pyrrolidine, piperidine,
picoline, trimethylamine, triethylamine, monoethanolamine,
diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine,
triethanolamine, diazabicyclooctane, diazabicyclononane,
diazabicycloundecene, tetramethylammonium hydroxide,
tetraethylammonium hydroxide, tetrapropylammonium hydroxide,
tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide,
benzyltrimethylammonium hydroxide, and benzyltriethylammonium
hydroxide.
Examples of the inorganic base include ammonia, sodium hydroxide,
potassium hydroxide, barium hydroxide, and calcium hydroxide. Among
these catalysts, metal chelate compounds, organic acids, and
inorganic acids are preferred, and they may be used singly or in
combination of two or more at the same time.
Examples of the organic solvent used in hydrolysis include
aliphatic hydrocarbon-based solvents such as:
n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane,
2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and
methylcyclohexane;
aromatic hydrocarbon-based solvents such as:
benzene, toluene, xylene, ethylbenzene, trimethylbenzene,
methylethylbenzene, n-propylbenzene, i-propylbenzene,
diethylbenzene, i-butylbenzene, triethylbenzene,
di-i-propylbenzene, n-amylnaphthalene, and trimethylbenzene;
monoalcohol-based solvents such as:
methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol,
sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol,
sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol,
2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol,
heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl
alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol,
trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl
alcohol, phenol, cyclohexanol, methylcyclohexanol,
3,3,5-trimethylcyclohexanol, benzil alcohol, phenylmethylcarbinol,
diacetone alcohol, and cresol; polyalcohol-based solvents such as:
ethylene glycol, propylene glycol, 1,3-butylene glycol,
pentanediol-2,4,2-methylpentanediol-2,4, hexanediol-2,5,
heptanediol-2,4,2-ethylhexanediol-1,3, diethylene glycol,
dipropylene glycol, triethylene glycol, tripropylene glycol, and
glycerol; ketone-based solvents such as: acetone, methyl ethyl
ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl
ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone,
ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone,
trimethylnonanone, cyclohexanone, methylcyclohexanone,
2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone,
and fenchone; ether-based solvents such as: ethyl ether, i-propyl
ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene
oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane,
dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol
monoethyl ether, ethylene glycol diethyl ether, ethylene glycol
mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene
glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether,
ethylene glycol dibutyl ether, diethylene glycol monomethyl ether,
diethylene glycol monoethyl ether, diethylene glycol diethyl ether,
diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl
ether, diethylene glycol mono-n-hexyl ether, ethoxy triglycol,
tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl
ether, propylene glycol monoethyl ether, propylene glycol
monopropyl ether, propylene glycol monobutyl ether, propylene
glycol monomethyl ether acetate, dipropylene glycol monomethyl
ether, dipropylene glycol monoethyl ether, dipropylene glycol
monopropyl ether; dipropylene glycol monobutyl ether, tripropylene
glycol monomethyl ether, tetrahydrofuran, and
2-methyltetrahydrofuran; ester-based solvents such as: diethyl
carbonate, methyl acetate, ethyl acetate, .gamma.-butyrolactone,
.gamma.-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl
acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate,
sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate,
2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate,
cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate,
methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl
ether acetate, ethylene glycol monoethyl ether acetate, diethylene
glycol monomethyl ether acetate, diethylene glycol monoethyl ether
acetate, diethylene glycol mono-n-butyl ether acetate, propylene
glycol monomethyl ether acetate, propylene glycol monoethyl ether
acetate, propylene glycol monopropyl ether acetate, propylene
glycol monobutyl ether acetate, dipropylene glycol monomethyl ether
acetate, dipropylene glycol monoethyl ether acetate, glycol
diacetate, methoxy triglycol acetate, ethyl propionate, n-butyl
propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate,
methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate,
diethyl malonate, dimethyl phthalate, and diethyl phthalate;
nitrogen-containing solvents such as: N-methylformamide,
N,N-dimethylformamide, N,N-diethylformamide, acetamide,
N-methylacetamide, N,N-dimethylacetamide. N-methylpropionamide, and
N-methylpyrrolidone; and sulfur-containing solvents such as:
dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene,
dimethylsulfoxide, sulfolane, and 1,3-propane sultone. These
solvents may be used singly or in combination of two or more.
In particular, ketone-based solvents such as acetone, methyl ethyl
ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl
ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone,
ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone,
trimethylnonanone, cyclohexanone, methylcyclohexanone,
2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone,
and fenchone are preferred in terms of storage stability of the
solution.
Bisphenol S or a bisphenol S derivative may be added as an
additive. The amount of bisphenol S or a bisphenol S derivative is
0.01 to 20 parts by mass, or 0.01 to 10 parts by mass, or 0.01 to 5
parts by mass with respect to 100 parts by mass of
polyorganosiloxane.
Examples of preferable bisphenol S or a bisphenol S derivative are
illustrated below.
##STR00026## ##STR00027## ##STR00028##
The film-forming composition of the present invention may contain a
curing catalyst. The curing catalyst acts as a curing catalyst when
a coating film containing polyorganosiloxane composed of a
hydrolysis-condensation product is heated and cured.
For example, ammonium salts, phosphines, phosphonium salts, or
sulfonium salts may be used as the curing catalyst.
Examples of the ammonium salts include
a quaternary ammonium salt having a structure of Formula (D-1):
##STR00029##
(where m is an integer of 2 to 11, n is an integer of 2 to 3,
R.sup.21 is an alkyl group or an aryl group, and Y.sub.A.sup.- is a
negative ion),
a quaternary ammonium salt having a structure of Formula (D-2):
R.sup.22R.sup.23R.sup.24R.sup.25N.sup.+Y.sub.A.sup.- Formula
(D-2)
(where each of R.sup.12, R.sup.23, R.sup.24 and R.sup.25 is an
alkyl group or an aryl group, N is a nitrogen atom, Y.sub.A.sup.-
is a negative ion, and R.sup.22, R.sup.23, R.sup.24, and R.sup.25
are each bonded to a nitrogen atom through a C--N bond),
a quaternary ammonium salt having a structure of Formula (D-3):
##STR00030##
(where each of R.sup.26 and R.sup.27 is an alkyl group or an aryl
group, and Y.sub.A.sup.- is a negative ion),
a quaternary ammonium salt having a structure of Formula (D-4);
##STR00031## (where R.sup.28 is an alkyl group or an aryl group,
and Y.sub.A.sup.- is a negative ion), a quaternary ammonium salt
having a structure of Formula (D-5):
##STR00032## (where each of R.sup.29 and R.sup.30 is an alkyl group
or an aryl group, and Y.sub.A.sup.- is a negative ion), and a
tertiary ammonium salt having a structure of Formula (D-6):
##STR00033##
(where m is an integer of 2 to 11, n is an integer of 2 to 3, H is
a hydrogen atom, and Y.sub.A.sup.- is a negative ion).
Examples of the phosphonium salts include a quaternary phosphonium
salt of Formula (D-7):
R.sup.31R.sup.32R.sup.33R.sup.34P.sup.+Y.sub.A.sup.- Formula
(D-7)
(where each of R.sup.31, R.sup.32, R.sup.33, and R.sup.34 is an
alkyl group or an aryl group, P is a phosphorus atom, Y.sub.A is a
negative ion, and R.sup.31, R.sup.32, R.sup.33, and R.sup.34 are
each bonded to a phosphorus atom through a C--P bond).
Examples of the sulfonium salts include a tertiary sulfonium salt
having a structure of Formula (D-8):
R.sup.35R.sup.36R.sup.37S.sup.+Y.sub.A.sup.- Formula (D-8)
(where each of R.sup.35, R.sup.36, and R.sup.37 is an alkyl group
or an aryl group, S is a sulfur atom, Y.sub.A.sup.- is a negative
ion, and R.sup.35, R.sup.36, and R.sup.37 are each bonded to a
sulfur atom through a C--S bond).
The compound of Formula (D-1) above is a quaternary ammonium salt
derived from amine, where m is an integer of 2 to 11, and n is an
integer of 2 to 3. R.sup.21 of this quaternary ammonium salt is a
C.sub.1-18, preferably C.sub.2-10 alkyl group or aryl group, and
examples include linear alkyl groups such as ethyl group, propyl
group, and butyl group, benzyl group, cyclohexyl group,
cyclohexylmethyl group, and dicyclopentadienyl group. Examples of
the negative ion (Y.sub.A.sup.-) include halogen ions such as
chlorine ion (Cl.sup.-), bromine ion (Br.sup.-), and iodine ion
(I.sup.-), and acid groups such as carboxylate (--COO.sup.-),
sulfonate (--SO.sub.3.sup.-), and alcoholate (--O.sup.-).
The compound of Formula (D-2) above is a quaternary ammonium salt
represented as
R.sup.22R.sup.23R.sup.24R.sup.25N.sup.+Y.sub.A.sup.-. R.sup.22,
R.sup.23, R.sup.24, and R.sup.25 of this quaternary ammonium salt
are a C.sub.1-18 alkyl group or aryl group, or a silane compound
bonded to a silicon atom through a Si--C bond. Examples of the
negative ion (Y.sub.A.sup.-) include halogen ions such as chlorine
ion (Cl.sup.-), bromine ion (Br.sup.-), and iodine ion (I.sup.-),
and acid groups such as carboxylate (--COO.sup.-), sulfonate
(--SO.sub.3.sup.-), and alcoholate (--O.sup.-). This quaternary
ammonium salt is commercially available, and examples include
tetramethylammonium acetate, tetrabutylammonium acetate,
triethylbenzylammonium chloride, triethylbenzylammonium bromide,
trioctylmethylammonium chloride, tributylbenzylammonium chloride,
and trimethylbenzylammonium chloride.
The compound of Formula (D-3) above is a quaternary ammonium salt
derived from 1-substituted imidazole, R.sup.26 and R.sup.27 are a
C.sub.1-18 alkyl group or aryl group, and the total carbon number
of R.sup.26 and R.sup.27 is preferably 7 or more. For example,
R.sup.26 may be a methyl group, an ethyl group, a propyl group, a
phenyl group, or a benzyl group, and R.sup.27 may be a benzyl
group, an octyl group, or an octadecyl group. Examples of the
negative ion (Y.sub.A.sup.-) include halogen ions such as chlorine
ion (Cl.sup.-), bromine ion (Br.sup.-), iodine ion (I.sup.-), and
acid groups such as carboxylate (--COO.sup.-), sulfonate
(--SO.sub.3.sup.-), and alcoholate (--O.sup.-). This compound may
be commercially obtained or may be produced, for example, by
reacting an imidazole-based compound such as 1-methylimidazole and
1-benzylimidazole with a halogenated alkyl or a halogenated aryl
such as benzyl bromide and methyl bromide.
The compound of Formula (D-4) above is a quaternary ammonium salt
derived from pyridine, R.sup.21 is a C.sub.1-18, preferably
C.sub.4-18 alkyl group or aryl group, and examples thereof include
butyl group, octyl group, benzyl group, and lauryl group. Examples
of the negative ion (Y.sub.A.sup.-) include halogen ions such as
chlorine ion (Cl.sup.-), bromine ion (Br.sup.-), and iodine ion
(I.sup.-), and acid groups such as carboxylate (--COO.sup.-),
sulfonate (--SO.sub.3.sup.-), and alcoholate (--O.sup.-). This
compound may be commercially obtained or may be produced, for
example, by reacting pyridine with a halogenated alkyl or a
halogenated aryl such as lauryl chloride, benzyl chloride, benzyl
bromide, methyl bromide, and octyl bromide. Examples of the
compound may include N-laurylpyridinium chloride and
N-benzylpyridinium bromide.
The compound of Formula (D-5) above is a quaternary ammonium salt
derived from a substituted pyridine such as picoline, R.sup.29 is a
C.sub.1-18, preferably .sub.4-18 alkyl group or aryl group, and
examples thereof include methyl group, octyl group, lauryl group,
and benzyl group. R.sup.30 is a C.sub.1-18 alkyl group or aryl
group. For example, in the case of a quaternary ammonium derived
from picoline, R.sup.30 is a methyl group. Examples of the negative
ion (Y.sub.A.sup.-) include halogen ions such as chlorine ion
(Cl.sup.-), bromine ion (Br.sup.-), and iodine ion (I.sup.-), and
acid groups such as carboxylate (--COO.sup.-), sulfonate
(--SO.sub.3.sup.-), and alcoholate (--O.sup.-). This compound may
be commercially obtained or may be produced, for example, by
reacting a substituted pyridine such as picoline with a halogenated
alkyl or a halogenated aryl such as methyl bromide, octyl bromide,
lauryl chloride, benzyl chloride, and benzyl bromide. Examples of
the compound include N-benzylpicolinium chloride,
N-benzylpicolinium bromide, and N-laurylpicolinium chloride.
The compound of Formula (D-6) above is a tertiary ammonium salt
derived from amine, where m is an integer of 2 to 11 and n is an
integer of 2 to 3. Examples of the negative ion (Y.sub.A.sup.-)
include halogen ions such as chlorine ion (Cl.sup.-), bromine ion
(Br.sup.-), and iodine ion (I.sup.-), and acid groups such as
carboxylate (--COO.sup.-), sulfonate (--SO.sub.3.sup.-), and
alcoholate (--O.sup.-). The compound may be produced by a reaction
of amine with weak acid such as carboxylic acid and phenol.
Examples of the carboxylic acid include formic acid and acetic
acid. When formic acid is used, the negative ion (Y.sub.A.sup.-) is
(HCOO.sup.-). When acetic acid is used, the negative ion
(Y.sub.A.sup.-) is (CH.sub.3COO.sup.-). When phenol is used, the
negative ion (Y.sub.A.sup.-) is (C.sub.6H.sub.5O.sup.-).
The compound of Formula (D-7) above is a quaternary phosphonium
salt having a structure of
R.sup.32R.sup.33R.sup.34P.sup.+Y.sub.A.sup.-. Each of R.sup.31,
R.sup.32, R.sup.33, and R.sup.34 is a C.sub.1-18 alkyl group or
aryl group, or a silane compound bonded to a silicon atom through a
Si--C bond. Preferably, three of four substituents in R.sup.31 to
R.sup.34 are phenyl groups or substituted phenyl groups, for
example, phenyl groups or tolyl groups, and the remaining one is a
C.sub.1-18 alkyl group, aryl group, or a silane compound bonded to
a silicon atom through a Si--C bond. Examples of the negative ion
(Y.sub.A.sup.-) include halogen ions such as chlorine ion
(Cl.sup.-), bromine ion (Br.sup.-), iodine ion (I.sup.-), and acid
groups such as carboxylate (--COO.sup.-), sulfonate
(--SO.sub.3.sup.-), and alcoholate (--O.sup.-). This compound is
commercially available, and examples thereof include halogenated
tetraalkylphosphoniums such as halogenated tetra-n-butylphosphonium
and halogenated tetra-n-propylphosphonium, halogenated
trialkylbenzylphosphoniums such as halogenated
triethylbenzylphosphonium, halogenated
triphenylmonoalkylphosphoniums such as halogenated
triphenylmethylphosphonium and halogenated
triphenylethylphosphonium, halogenated
triphenylbenzylphospsphoniums, halogenated tetraphenylphosphoniums,
halogenated tritolylmonoarylphosphoniums, and halogenated
tritolylmonoalkylphosphoniumns (where the halogen atom is a
chlorine atom or a bromine atom). In particular, halogenated
triphenylmonoalkylphosphoniumns such as halogenated
triphenylmethylphosphonium and halogenated
triphenylethylphosphonium, halogenated
triphenylmonoarylphosphoniums such as halogenated
triphenylbenzylphosphonium, halogenated
tritolylmonoarylphosphoniums such as halogenated
tritolylmonophenylphosphonium, and halogenated
tritolylmonoalkylphosphoniums such as halogenated
tritolylmonomethylphosphonium (where the halogen atom is a chlorine
atom or a bromine atom) are preferable.
Examples of the phosphines include primary phosphines such as
methylphosphine, ethylphosphine, propylphosphine,
isopropylphosphine, isobutylphosphine, and phenylphosphine,
secondary phosphines such as dimethylphosphine, diethylphosphine,
diisopropylphosphine, diisoamylphosphine, and diphenylphosphine,
and tertiary phosphines such as trimethylphosphine,
triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and
dimethylphenylphosphine.
The compound of Formula (D-8) above is a tertiary sulfonium salt
having a structure of R.sup.35R.sup.36R.sup.37S.sup.+Y.sub.A.sup.-.
R.sup.35, R.sup.36, and R.sup.37 are a C.sub.1-18 alkyl group or
aryl group, or a silane compound bonded to a silicon atom through a
Si--C bond. Preferably, three of four substituents in R.sup.35 to
R.sup.37 are phenyl groups or substituted phenyl groups, such as
phenyl groups or tolyl groups, and the remaining one is a
C.sub.1-18 alkyl group or aryl group. Examples of the negative ion
(Y.sub.A.sup.-) include halogen ions such as chlorine ion
(Cl.sup.-), bromine ion (Br.sup.-), and iodine ion (I.sup.-), and
acid groups such as carboxylate (--COO.sup.-), sulfonate
(--SO.sub.3.sup.-), alcoholate (--O.sup.-), maleic acid anion, and
nitric acid anion. The compound is commercially available, and
examples thereof include halogenated tetraalkylsulfoniums such as
halogenated tri-n-butylsulfonium, halogenated
tri-n-propylsulfonium, halogenated trialkylbenzylsulfoniums such as
halogenated diethylbenzylsulfonium, halogenated
diphenylmonoalkylsulfoniums such as halogenated
diphenylmethylsulfonium and halogenated diphenylethylsulfinium,
halogenated triphenylsulfoniums (where the halogen atom is a
chlorine atom or a bromine atom), tetraalkylphosphonium
carboxylates such as tri-n-butylsulfonium carboxylate and
tri-n-propylsulfonium carboxylate, trialkylbenzylsulfonium
carboxylates such as diethylbenzylsulfonium carboxylate,
diphenylmonoalkylsulfonium carboxylates such as
diphenylmethylsulfonium carboxylate and diphenylethylsulfonium
carboxylate, and triphenylsulfonium carboxylates. Halogenated
triphenylsulfonium and triphenylsulfonium carboxylate can
preferably be used.
In the present invention, a nitrogen-containing silane compound can
be added as a curing catalyst. Examples of the nitrogen-containing
silane compound include imidazole ring-containing silane compounds
such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.
The amount of the curing catalyst is 0.01 to 10 parts by mass, or
0.01 to 5 parts by mass, or 0.01 to 3 parts by mass with respect to
100 parts by mass of polyorganosiloxane.
The hydrolysis-condensation product (polymer) obtained by
hydrolyzing and condensing the hydrolyzable silane in a solvent
using a catalyst can be subjected to reduced-pressure distillation
to simultaneously remove the by-product alcohol, the used
hydrolysis catalyst, and water. The acid or base catalyst used in
the hydrolysis can be removed through neutralization or ion
exchange. An organic acid, water, alcohol, or a combination thereof
can be added to the film-forming composition of the present
invention in order to stabilize the film-forming composition
including the hydrolysis-condensation product.
Examples of the organic acid above include oxalic acid, malonic
acid, methylmalonic acid, succinic acid, maleic acid, malic acid,
tartaric acid, phthalic acid, citric acid, glutaric acid, citric
acid, lactic acid, and salicylic acid. Among those, preferable
examples include oxalic acid and maleic acid. The amount of the
organic acid added is 0.1 to 5.0 parts by mass with respect to 100
parts by mass of the condensation product (polyorganosiloxane). The
water added may be pure water, ultrapure water, ion exchange water,
and the like, and the amount added can be 1 to 20 parts by mass
with respect to 100 parts by mass of the film-forming
composition.
The alcohol added is preferably the one easily evaporated by
heating after the application, and examples thereof include
methanol, ethanol, propanol, isopropanol, and butanol. The amount
of alcohol added can be 1 to 20 parts by mass with respect to 100
parts by mass of the film-forming composition.
The film-forming composition of the present invention can include,
in addition to the components above, an organic polymer compound, a
photoacid generator, a surfactant, and the like, as necessary.
The organic polymer compound is not limited to a particular
compound, and various kinds of organic polymers may be used. A
condensation polymer, an addition polymer, and the like can be
used. An addition polymer and a condensation polymer such as
polyester, polystyrene, polyimide, acrylic polymer, methacrylic
polymer, polyvinyl ether, phenol novolac, naphthol novolac,
polyether, polyamide, and polycarbonate can be used. An organic
polymer having an aromatic ring structure such as benzene ring,
naphthalene ring, anthracene ring, triazine ring, quinoline ring,
and quinoxaline ring functioning as a light-absorbing moiety is
preferably used.
Examples of such an organic polymer compound include addition
polymers including addition polymerizable monomers as its
structural unit, such as benzyl acrylate, benzyl methacrylate,
phenyl acrylate, naphthyl acrylate, anthryl methacrylate,
anthrylmethyl methacrylate, styrene, hydroxystyrene, benzyl vinyl
ether, and N-phenylmaleimide, and condensation polymers such as
phenol novolac and naphthol novolac.
When an addition polymer is used as the organic polymer compound,
the polymer compound may be a homopolymer or may be a copolymer. In
production of the addition polymer, an addition polymerizable
monomer is used. Examples of such an addition polymerizable monomer
include acrylic acids, methacrylic acids, acrylic acid ester
compounds, methacrylic acid ester compounds, acrylamide compounds,
methacrylamide compounds, vinyl compounds, styrene compounds,
maleimide compounds, maleic anhydrides, and acrylonitrile.
Examples of the acrylic acid ester compound include methyl
acrylate, ethyl acrylate, normal hexyl acrylate, isopropyl
acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate,
anthrylmethyl acrylate, 2-hydroxyethyl acrylate,
3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate,
2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate,
2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl
acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl
acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone,
3-acryloxypropyltriethoxysilane, and glycidyl acrylate.
Examples of the methacrylic acid ester compound include methyl
methacrylate, ethyl methacrylate, normal hexyl methacrylate,
isopropyl methacrylate, cyclohexyl methacrylate, benzyl
methacrylate, phenyl methacrylate, anthrylmethyl methacrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl
methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl
methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl
methacrylate, 2-methyl-2-adamantyl methacrylate.
5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone,
3-methacryloxypropyltriethoxysilane, glycidyl methacrylate,
2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and
bromophenyl methacrylate.
Examples of the acrylamide compound include acrylamide,
N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide,
N-phenylacrylamide, N,N-dimethylacrylamide, and
N-anthrylacrylamide.
Examples of the methacrylamide compound include methacrylamide,
N-methylmethacrylamide, N-ethylmethacrylamide,
N-benzylmethacrylamide, N-phenylmethacrylamide,
N,N-dimethylmethacrylamide, and N-anthrylacrylamide.
Examples of the vinyl compound include vinyl alcohol,
2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether,
benzyl vinyl ether, vinyl acetate, vinyltrimethoxysilane,
2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether,
vinylnaphthalene, and vinylanthracene.
Examples of the styrene compound include styrene, hydroxystyrene,
chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and
acetylstyrene.
Examples of the maleimide compound include maleimide,
N-methylmaleimide, N-phenylrnaleimide, N-cyclohexylmaleimide,
N-benzylmaleimide, and N-hydroxyethylmaleimide.
When a condensation polymer is used as the polymer, examples of
such a polymer include a condensation polymer of a glycol compound
and a dicarboxylic acid compound. Examples of the glycol compound
include diethylene glycol, hexamethylene glycol, and butylene
glycol. Examples of the dicarboxylic acid compound include succinic
acid, adipic acid, terephthalic acid, and maleic anhydride. Other
examples include polyesters, polyamides, and polyimides such as
polypyromellitimide, poly(p-phenylene terephthalamide),
polybutylene terephthalate, and polyethylene terephthalate.
When the organic polymer compound contains hydroxy group, this
hydroxy group can form a cross-linking reaction with
polyorganosiloxane.
As the organic polymer compound, a polymer compound having a weight
average molecular weight of, for example, 1000 to 1000000, or 3000
to 300000, or 5000 to 200000, or 10000 to 100000 can be used.
The organic polymer compounds may be used singly or may be used in
combination of two or more.
When the organic polymer compound is used, the amount of the
organic polymer compound is 1 to 200 parts by mass, or 5 to 100
parts by mass, or 10 to 50 parts by mass, or 20 to 30 parts by mass
with respect to 100 parts by mass of the condensation product
(polyorganosiloxane).
The film-forming composition of the present invention may contain
an acid generator.
Examples of the acid generator include thermal acid generators and
photoacid generators.
Examples of the photoacid generator included in the film-forming
composition of the present invention include onium salt compounds,
sulfonimide compounds, and disulfonyl diazomethane compounds.
Examples of the onium salt compound include iodonium salt compounds
such as diphenyliodonium hexafluorophosphate, diphenyliodonium
trifluorornethanesulfonate, diphenyliodonium nonafluoro
normalbutanesulfonate, diphenyliodonium perfluoro
normaloctanesulfonate, diphenyliodonium camphorsulfonate,
bis(4-tert-butylphenyl)iodonium camphorsulfonate, and
bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and
sulfonium salt compounds such as triphenylsulfonium
hexafluoroantimonate, triphenylsulfonium nonafluoro
normalbutanesulfonate, triphenylsulfonium camphorsulfonate, and
triphenylsulfonium trifluoromethanesulfonate.
Examples of the sulfonimide compound include
N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro normal
butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide,
and N-(trifluoromethanesulfonyloxy)naphthalimide.
Examples of the disulfonyl diazomethane compound include
bis(trifluoromethylsulfonyl)diazomethane,
bis(cyclohexylsulfonyl)diazomethane,
bis(phenylsulfonyl)diazomethane,
bis(p-toluenesulfonyl)diazomethane,
bis(2,4-dimethylbenzenesulfonyl)diazomethane, and
methylsulfonyl-p-toluenesulfonyldiazomethane.
The photoacid generators may be used singly or may be used in
combination of two or more.
When a photoacid generator is used, the amount of the photoacid
generator is 0.01 to 5 parts by mass, or 0.1 to 3 parts by mass, or
0.5 to 1 part by mass with respect to 100 parts by mass of the
condensation product (polyorganosiloxane).
The surfactant is effective for suppressing pinholes, striation,
and the like when the film-forming composition of the present
invention is applied on a substrate as the resist underlayer
film-forming composition for lithography.
Examples of the surfactant included in the film-forming composition
of the present invention include polyoxyethylene alkyl ethers such
as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether,
polyoxyethylene alkyl aryl ethers such as polyoxyethylene
octylphenol ether, and polyoxyethylene nonylphenol ether,
polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty
acid esters such as sorbitan monolaurate, sorbitan monopalmitate,
sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and
sorbitan tristearate, nonionic surfactants such as polyoxyethylene
sorbitan fatty acid esters such as polyoxyethylene sorbitan
monolaurate, polyoxyethylene sorbitan monopalmitate,
polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan
trioleate, and polyoxyethylene sorbitan tristearate, fluorine-based
surfactants such as trade name: iFTOP EF301, EF303, EF352
(manufactured by Tobhkem Products Corp.), trade name: MEGAFACE
F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC
Corporation), Fluorad FC430, FC431 (manufactured by Sumitomo 3M
Limited), trade name: AsahiGuard AG710, Surtlon S-382, SC101,
SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co.,
Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu
Chemical Co., Ltd.). These surfactants may be used singly or may be
used in combination of two or more. When a surfactant is used, the
amount of the surfactant is 0.0001 to 5 parts by mass, or 0.001 to
1 part by mass, or 0.01 to 1 part by mass with respect to 100 parts
by mass of the condensation product (polyorganosiloxane).
A rheology controlling agent, an adhesion assistant, and the like
may further be added to the film-forming composition of the present
invention. The rheology controlling agent is effective for
improving the fluidity of the film-forming composition. The
adhesion assistant is effective for improving the adhesion between
the semiconductor substrate or the resist and the underlayer
film.
The solvent used in the film-forming composition of the present
invention may be any solvent that can dissolve the solid contents
above. Examples of such a solvent include methyl cellosolve
acetate, ethyl cellosolve acetate, propylene glycol, propylene
glycol monomethyl ether, propylene glycol monoethyl ether, methyl
isobutyl carbinol, propylene glycol monobutyl ether, propylene
glycol monomethyl ether acetate, propylene glycol monoethyl ether
acetate, propylene glycol monopropyl ether acetate, propylene
glycol monobutyl ether acetate, toluene, xylene, methyl ethyl
ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxy propionate,
ethyl 2-hydroxy-2-methyl propionate, ethyl ethoxy acetate, ethyl
hydroxy acetate, methyl 2-hydroxy-3-methylbutanoate, methyl
3-methoxy propionate, ethyl 3-methoxy propionate, ethyl 3-ethoxy
propionate, methyl 3-ethoxy propionate, methyl pyruvate, ethyl
pyruvate, ethylene glycol monomethyl ether, ethylene glycol
monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol
monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene
glycol monoethyl ether acetate, ethylene glycol monopropyl ether
acetate, ethylene glycol monobutyl ether acetate, diethylene glycol
dimethyl ether, diethylene glycol diethyl ether, diethylene glycol
dipropyl ether, diethylene glycol dibutyl ether, propylene glycol
monomethyl ether, propylene glycol dimethyl ether, propylene glycol
diethyl ether, propylene glycol dipropyl ether, propylene glycol
dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate,
butyl lactate, isobutyl lactate, methyl formate, ethyl formate,
propyl formate, isopropyl formate, butyl formate, isobutyl formate,
amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl
acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl
propionate, propyl propionate, isopropyl propionate, butyl
propionate, isobutyl propionate, methyl butyrate, ethyl butyrate,
propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl
butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate,
methyl 3-methoxy-2-methylpropionate, methyl
2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl
ethoxyacetate, methyl 3-methoxypropionate, ethyl
3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl
acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate,
3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl
butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl
ketone, methylpropyl ketone, methylbutyl ketone, 2-heptanone,
3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide,
N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone,
4-methyl-2-pentanol, and .gamma.-butyrolactone. These solvents may
be used singly or may be used in combination of two or more.
In the present invention, the film-forming composition can be used
as a resist underlayer film-forming composition for use in the
lithography process.
A resist underlayer film-forming composition including the
film-forming composition of the present invention is applied on a
substrate used in production of semiconductor devices (for example,
a silicon wafer substrate, a silicon/silicon dioxide-coated
substrate, a silicon nitride substrate, a glass substrate, an ITO
substrate, a polyimide substrate, and a low dielectric constant
material (low-k material)-coated substrate) by an appropriate
coating method such as a spinner and a coater and is thereafter
baked to form a resist underlayer film. The conditions of baking
are appropriately selected from the baking temperature of
80.degree. C. to 250.degree. C. and the baking time of 0.3 to 60
minutes. Preferably, the baking temperature is 150.degree. C. to
250.degree. C. and the baking time is 0.5 to 2 minutes. The film
thickness of the resist underlayer film formed in the present
invention is, for example, 10 to 1000 nm, or 20 to 500 nm, or 50 to
300 nm, or 100 to 200 nm.
Subsequently, for example, a photoresist layer is formed on the
resist underlayer film. The photoresist layer can be formed by a
well-known method, that is, by applying a photoresist composition
solution on the underlayer film and baking. The film thickness of
the photoresist is, for example, 50 to 10000 nm, or 100 to 2000 nm,
or 200 to 1000 nm.
In the present invention, after an organic underlayer film is
formed on a substrate, the resist underlayer film of the present
invention can be formed thereon and then covered with a
photoresist. The pattern width of the photoresist is thus narrower,
and the substrate can be processed by selecting an appropriate
etching gas even when a thin photoresist is applied in order to
prevent pattern collapse. For example, the resist underlayer film
of the present invention can be processed using fluorine-based gas
as an etching gas with a sufficiently high etching rate with
respect to the photoresist. The organic underlayer film can be
processed using oxygen-based gas as an etching gas with a
sufficiently high etching rate with respect to the resist
underlayer film of the present invention. Furthermore, the
substrate can be processed using fluorine-based gas as an etching
gas with a sufficiently high etching rate with respect to the
organic underlayer film.
The photoresist formed on the resist underlayer film of the present
invention is not limited to a particular one as long as photoresist
is sensitive to light used for exposure. Either of a negative-type
photoresist and a positive-type photoresist can be used. Examples
of the photoresist include: a positive-type photoresist composed of
a novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester;
a chemical amplification-type photoresist composed of a binder
having a group decomposed by an acid to increase the alkali
dissolving rate, and a photoacid generator; a chemical
amplification-type photoresist composed of a low-molecular compound
decomposed by an acid to increase the alkali dissolving rate of a
photoresist, an alkali-soluble binder, and a photoacid generator;
and a chemical amplification-type photoresist composed of a binder
having a group decomposed by an acid to increase the alkali
dissolving rate, a low-molecular compound decomposed by an acid to
increase the alkali dissolving rate of a photoresist, and a
photoacid generator. Examples of the photoresist include trade
name: APEX-E manufactured by Shipley Company. L.L.C., trade name:
PAR710 manufactured by Sumitomo Chemical Co., Ltd., and trade name:
SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. The examples
also include fluorine atom-containing polymer-based photoresists
described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE,
Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374
(2000).
Next, the exposure is performed through a predetermined mask. For
the exposure, a Krf excimer laser (wavelength: 248 nm), an ArF
excimer laser (wavelength: 193 nm), an F2 excimer laser
(wavelength: 157 nm), and the like can be used. After the exposure,
post exposure bake can also be performed, if necessary. The post
exposure bake is performed under conditions appropriately selected
from the baking temperature of 70.degree. C. to 150.degree. C. and
the baking time of 0.3 to 10 minutes.
In the present invention, a resist for electron beam lithography or
a resist for EUV lithography can be used as the resist, instead of
the photoresist. As the electron beam resist, either of a positive
type and a negative type can be used. Examples of the electron beam
resist include: a chemical amplification-type resist composed of an
acid generator and a binder having a group decomposed by an acid to
change the alkali dissolving rate; a chemical amplification-type
resist composed of an alkali-soluble binder, an acid generator, and
a low-molecular compound decomposed by an acid to change the alkali
dissolving rate of a resist; a chemical amplification-type resist
composed of an acid generator, a binder having a group decomposed
by an acid to change the alkali dissolving rate, and a
low-molecular compound decomposed by an acid to change the alkali
dissolving rate of a resist; a non-chemical amplification-type
resist composed of a binder having a group decomposed by an
electron beam to change the alkali dissolving rate; and a
non-chemical amplification-type resist composed of a binder having
a moiety broken by an electron beam to change the alkali dissolving
rate. Also, in the case of using these electron beam resists, a
resist pattern can be formed using an electron beam as the
radiation source in the same manner as in the case of using a
photoresist.
Examples of the EUV resist include methacrylate resin-based
resists.
Subsequently, development is performed using a developer (for
example, alkaline developer). By doing so, for example, when a
positive photoresist is used, the photoresist of the exposed
portion is removed, and the pattern of the photoresist is
formed.
Examples of the developer include alkaline aqueous solutions such
as: aqueous solutions of alkali metal hydroxides such as potassium
hydroxide and sodium hydroxide; aqueous solutions of quaternary
ammonium hydroxides such as tetramethylammonium hydroxide,
tetraethylammonium hydroxide, and choline; and aqueous solutions of
amines such as ethanolamine, propylamine, and ethylenediamine. In
addition, a surfactant and the like may be added to these
developers. The conditions for the development are selected
appropriately from the temperature of 5 to 50.degree. C. and the
time of 10 to 600 seconds.
In the present invention, an organic solvent can be used as a
developer. Development is performed using a developer (solvent)
after exposure. By doing so, for example, when a positive
photoresist is used, the photoresist of the unexposed portion is
removed, and the pattern of the photoresist is formed.
Examples of the developer include methyl acetate, butyl acetate,
ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate,
ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol
monomethyl ether acetate, ethylene glycol monoethyl ether acetate,
ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl
ether acetate, ethylene glycol monophenyl ether acetate, diethylene
glycol monomethyl ether acetate, diethylene glycol monopropyl ether
acetate, diethylene glycol monoethyl ether acetate, diethylene
glycol monophenyl ether acetate, diethylene glycol monobutyl ether
acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate,
4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate,
3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether
acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl
acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate,
2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl
acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl
acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl
acetate, propylene glycol diacetate, methyl formate, ethyl formate,
butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl
lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl
pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl
acetoacetate, ethyl acetoacetate, methyl propionate, ethyl
propionate, propyl propionate, isopropyl propionate, methyl
2-hydroxypropionate, ethyl 2-hydroxypropionate,
methyl-3-methoxypropionate, ethyl-3-methoxypropionate,
ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. In
addition, a surfactant and the like may be added to these
developers. The development conditions are selected appropriately
from the temperature of 5 to 50.degree. C. and the time of 10 to
600 seconds.
Then, using the pattern of the thus formed photoresist (upper
layer) as a protective film, the resist underlayer film of the
present invention (intermediate layer) is removed, and then using
the patterned film including the photoresist and the resist
underlayer of the present invention (intermediate layer) as a
protective film, the organic underlayer film (underlayer) is
removed. Finally, using the patterned resist underlayer film of the
present invention (intermediate layer) and the organic underlayer
film (underlayer) as a protective film, the semiconductor substrate
is processed.
First, the resist underlayer film of the present invention
(intermediate layer) at the part where the photoresist is removed
is removed by dry etching to expose the semiconductor substrate. In
the dry etching of the resist underlayer film of the present
invention, gas such as tetrafluoromethane (CF.sub.4),
perfluorocyclobutane (C.sub.4F.sub.8), perfluoropropane
(C.sub.3F.sub.8), trifluoromethane, carbon monoxide, argon, oxygen,
nitrogen, sulfur hexafluoride, difluoromethane, nitrogen
trifluoride and chlorine trifluoride, chlorine, trichloroborane and
dichloroborane can be used. In the dry etching of the resist
underlayer film, halogen-based gas is preferably used. In the dry
etching using halogen-based gas, basically, a photoresist composed
of an organic substance is less removed. By contrast, the resist
underlayer film of the present invention including many silicon
atoms is removed quickly by halogen-based gas. This can suppress
reduction in film thickness of the photoresist due to the dry
etching of the resist underlayer film. As a result, the photoresist
can be used in the form of a thin film. The dry etching of the
resist underlayer film is preferably performed using fluorine-based
gas. Examples of the fluorine-based gas include tetrafluoromethane
(CF.sub.4), perfluorocyclobutane (C.sub.4F.sub.8), perfluoropropane
(C.sub.3F.sub.8), trifluoromethane, and difluoromethane
(CH.sub.2F.sub.2).
Subsequently, using the patterned film including the photoresist
and the resist underlayer film of the present invention as a
protective film, the organic underlayer film is removed. The
organic underlayer film (underlayer) preferably undergoes dry
etching using oxygen-based gas. This is because the resist
underlayer film of the present invention including many silicon
atoms is less removed by dry etching using oxygen-based gas.
Finally, the semiconductor substrate is processed. The
semiconductor substrate is preferably processed by dry etching
using fluorine-based gas.
Examples of the fluorine-based gas include tetrafluoromethane
(CF.sub.4), perfluorocyclobutane (C.sub.4F.sub.8), perfluoropropane
(C.sub.3F.sub.8), trifluoromethane, and difluoromethane
(CH.sub.2F.sub.2).
As the upper layer on the resist underlayer film of the present
invention, an organic anti-reflective coating may be formed before
formation of a photoresist. An anti-reflective coating composition
used for the anti-reflective coating is not limited to a particular
one, and may be appropriately selected from various anti-reflective
coating compositions that have been commonly used for lithography
process. The anti-reflective coating can be formed by a commonly
used method, for example, coating with a spinner and a coater and
baking.
The substrate coated with the resist underlayer film-forming
composition composed of the film-forming composition of the present
invention may have an organic or inorganic anti-reflective coating
formed on the surface by CVD or the like, and the resist underlayer
film of the present invention may be formed thereon.
The resist underlayer film formed of the resist underlayer
film-forming composition of the present invention may have
absorption of light depending on the wavelength of light used in
the lithography process. In such a case, the resist underlayer film
may function as an anti-reflective coating having the effect of
preventing reflection light from the substrate. In addition, the
resist underlayer film of the present invention may also be used as
a layer for preventing interaction between the substrate and the
photoresist, a layer having the function of preventing a material
used for a photoresist or a substance produced at the time of
exposing a photoresist to light from having an adverse effect on a
substrate, a layer having the function of preventing diffusion of a
substance generated from the substrate during heating and baking
into the overlying photoresist, a barrier layer for reducing the
poisoning effect of the photoresist layer by the semiconductor
substrate dielectric layer, and the like.
The resist underlayer film formed of the resist underlayer
film-forming composition of the present invention can be applied to
a substrate having via holes used in the dual damascene process and
can be used as a hole-filling material (filler) capable of filling
the holes without vacancy. It can also be used as a planarizing
material for planarizing the surface of an uneven semiconductor
substrate.
As the underlayer film for the EUV resist, it can also be used for
the following purposes in addition to the function as a hard mask.
The resist underlayer film-forming composition can be used as an
underlayer anti-reflective coating for the EUV resist that can
prevent reflection of undesirable exposure light in EUV exposure
(wavelength of 13.5 nm), for example, the above-noted UV or DUV
(ArF light, KrF light), from the substrate or the interface,
without intermixing with the EUV resist. The underlayer for the EUV
resist can efficiently prevent reflection. In the case of using as
an EUV resist underlayer film, the process can be performed in the
same manner as the underlayer film for photoresist.
The present invention relates to a hydrolyzable silane of Formula
(1'). R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4-(a+b) Formula
(1')
In Formula (1'), R.sup.1 is an organic group of Formula (2') and is
bonded to a silicon atom through a Si--C bond or a Si--O bond.
##STR00034##
R.sup.2 is an alkyl group, an aryl group, a halogenated alkyl
group, a halogenated aryl group, an alkoxyaryl group, an alkenyl
group, or an organic group having an epoxy group, an acryloyl
group, a methacryloyl group, a mercapto group, an amino group, or a
cyano group, or a combination thereof and is bonded to a silicon
atom through a Si--C bond. R.sup.3 is an alkoxy group, an acyloxy
group, or a halogen group. Then, a is an integer of 1, b is an
integer of 0 to 2, and a+b is an integer of 1 to 3.
In Formula (2'), R.sup.4 is a hydrogen atom, a C.sub.1-10 alkyl
group, or an acyl group, R.sup.5 is a hydrogen atom, a C.sub.1-10
alkyl group, or a C.sub.1-10 alkyl group having a C.sub.1-10 alkoxy
group, R.sup.6 is a C.sub.1-10 alkyl group, n1 is an integer of 0
to 10, n2 is an integer of 0 or 1, n3, n4, and n5 are integers,
where n3 satisfies 1.ltoreq.n3.ltoreq.5, n4 satisfies
0.ltoreq.n4.ltoreq.4, and n5 satisfies 0.ltoreq.n5.ltoreq.4. Then,
k1 is a bond end with a silicon atom when n1 is 1 to 10, k2 is a
bond end with a silicon atom when n1 is 0 and n2 is 1, and k3 is a
bond end with a silicon atom when n and n2 are 0.
In the k1 portion, the one bonded to a silicon atom can be
selected.
Examples of the hydrolyzable silane compound of Formula (1')
include the compounds of Formula (1-1), Formula (1-2), Formula
(1-3), Formula (1-5), Formula (1-6), Formula (1-7), Formula (1-8),
and Formula (1-10) above. Other examples include
4-(trimethoxysilyl)benzyl acetate and 4-(triethoxysilyl)benzyl
acetate.
A compound in which n2 is an integer of 1 in Formula (1') can be
exemplified.
EXAMPLES
Synthesis of Compound 1
##STR00035##
To a 1000-ml eggplant-shaped flask with a magnetic stirrer, 20.0 g
of hydroxybenzyl alcohol and 400.0 g of ethanol were added and
dissolved. To this solution, 0.32 g of concentrated sulfuric acid
was added and heated for reflux for 20 hours. After the product was
returned to room temperature and neutralized with sodium hydroxide,
ethanol was removed by evaporation. The product was put into a
300-ml three-necked flask, to which 6.44 g of sodium hydroxide, 40
g of toluene, and 40 g of N-methylpyrrolidone (which may
hereinafter be abbreviated as NMP) were added to allow a reaction
to proceed for 4 hours while removing water and toluene in an oil
bath at 130.degree. C. Then, 34.28 g of chloromethyltriethoxysilane
was added dropwise, and heating and stirring was performed at
130.degree. C. for 4 hours. The resultant solution was returned to
room temperature and put into a separating funnel, to which 120 g
of toluene and 90 g of water were added to wash the organic phase.
The washing was repeatedly performed three times. Next, the organic
phase was dried with addition of magnesium sulfate and then
filtered, and the solvent was removed by evaporation to yield a
crude product. Subsequently, the crude product was purified by
reduced-pressure distillation to yield 15 g of Compound 1 of
interest.
.sup.1H-NMR (500 MHz, DMSO-d.sub.6): 1.13 ppm (t, 3H), 1.19 ppm (t,
9H), 3.43 ppm (q, 2H), 3.68 ppm (s, 2H), 3.86 ppm (q, 6H), 4.36 ppm
(s, 2H), 6.95 ppm (d, 2H), 7.22 ppm (d, 2H)
Synthesis of Compound 2
##STR00036##
To a 1000-ml eggplant-shaped flask with a magnetic stirrer, 30.0 g
of 2,6-bis(hydroxymethyl)-p-cresol and 600.0 g of methanol were
added and dissolved. To this solution, 0.35 g of concentrated
sulfuric acid was added and heated for reflux for 20 hours. After
the solution was returned to room temperature and neutralized with
sodium hydroxide, methanol was removed by evaporation. The product
was put into a 300-ml three-necked flask, to which 7.13 g of sodium
hydroxide, 60 g of toluene, and 60 g of NMP were added to allow a
reaction to proceed for 4 hours while removing water and toluene in
an oil bath at 130.degree. C. Then, 35.54 g of
3-chloropropyltrimethoxysilane was added dropwise, and heating and
stirring was performed at 130.degree. C. for 4 hours. The resultant
solution was returned to room temperature and put into a separating
funnel, to which 120 g of toluene and 90 g of water were added to
wash the organic phase. The washing was repeatedly performed three
times. Next, the organic phase was dried with addition of magnesium
sulfate and then filtered, and the solvent was removed by
evaporation to yield a crude product. Subsequently, the crude
product was purified by reduced-pressure distillation to yield 5 g
of Compound 2 of interest.
.sup.1H-NMR (500 MHz, DMSO-d.sub.6): 0.70 ppm (t, 2H), 1.74 ppm
(quin, 2H), 2.22 ppm (s, 3H), 3.27 ppm (s, 6H), 3.47 ppm (s, 9H),
3.67 ppm (t, 2H), 4.35 ppm (s, 4H), 7.07 ppm (s, 2H)
Synthesis of Compound 3
##STR00037##
To a 1000-ml eggplant-shaped flask with a magnetic stirrer, 20.0 g
of vanillyl alcohol and 400.0 g of methanol were added and
dissolved. To this solution, 0.25 g of concentrated sulfuric acid
was added and heated for reflux for 1 hour. After the solution was
returned to room temperature and neutralized with sodium hydroxide,
methanol was removed by evaporation. The product was put into a
300-ml three-necked flask, to which 5.19 g of sodium hydroxide, 40
g of toluene, and 40 g of NMP were added to allow a reaction to
proceed for 4 hours while removing water and toluene in an oil bath
at 130.degree. C. Then, 27.60 g of chloromethyltriethoxysilane was
added dropwise, and heating and stirring was performed at
130.degree. C. for 4 hours. The resultant solution was returned to
room temperature and put into a separating funnel, to which 120 g
of toluene and 90 g of water were added to wash the organic phase.
The washing was repeatedly performed three times. Next, the organic
phase was dried with addition of magnesium sulfate and then
filtered, and the solvent was removed by evaporation to yield a
crude product. Subsequently, the crude product was purified by
reduced-pressure distillation to yield 15 g of Compound 3 of
interest.
.sup.1H-NMR (500 MHz, DMSO-d.sub.6): 1.20 ppm (t, 9H), 3.26 ppm (s,
3H), 3.68 ppm (s, 2H), 3.75 ppm (s, 3H), 3.87 ppm (q, 6H), 4.32 ppm
(s, 2H), 6.83 ppm (d, 1H), 6.89 ppm (s, 1H), 7.00 ppm (d, 2H)
Synthesis of Compound 4
##STR00038##
To a 300-ml three-necked flask with a magnetic stirrer, 40 g of
4-chloromethylphenyltrimethoxysilane (manufactured by Gelest Inc.)
and 80 g of NMP were added and heated to 130.degree. C. and stirred
in an oil bath. To this solution, 8.76 g of sodium methoxide was
added, and heating and stirring was performed at 130.degree. C. for
4 hours. The resultant solution was returned to room temperature
and put into a separating funnel, to which 200 g of toluene and 100
g of water were added to wash the organic phase. The washing was
repeatedly performed three times. Next, the organic phase was dried
with addition of magnesium sulfate and then filtered, and the
solvent was removed by evaporation to yield a crude product.
Subsequently, the crude product was purified by reduced-pressure
distillation to yield 5 g of Compound 4 of interest.
.sup.1H-NMR (500 MHz, DMSO-d.sub.6): 3.30 ppm (s, 3H), 3.53 ppm (s,
9H), 4.43 ppm (s, 2H), 7.37 ppm (d, 2H), 7.56 ppm (d, 2H)
Synthesis of Compound 5
##STR00039##
To a 1000-ml eggplant-shaped flask, 20.00 g (0.119 mol) of
2,6-bis(hydroxymethyl)-p-cresol, 400 g of methanol, and 0.23 g
(0.002 mol) of concentrated sulfuric acid were put and heated in a
reflux state for 20 hours. After the product was returned to room
temperature and neutralized with sodium hydroxide, methanol was
removed by evaporation. The product was put into a 300-ml
three-necked flask, to which 40 g of toluene, 40 g of
N-methylpyrrolidone, and 4.99 g (0.125 mol) of sodium hydroxide
were added to allow a reaction to proceed for 4 hours while
removing water and toluene in an oil bath at 130.degree. C. Then,
25.30 g (0.119 mol) of chloromethyltriethoxysilane was added
dropwise to allow a reaction to proceed at 120.degree. C. for 4
hours. After the reaction solution was subjected to
liquid-separation extraction with toluene and acetone, and water,
the organic solvent was removed with an evaporator to yield a crude
product. The crude product was distilled under reduced pressure to
obtain the compound of interest.
.sup.1H-NMR (500 MHz, DMSO-d.sub.6): 1.23 ppm (t, 9H), 2.26 ppm (s,
3H), 3.31 ppm (s, 6H), 3.59 ppm (s, 2H), 3.89 ppm (q, 6H), 4.40 ppm
(s, 4H), 7.10 ppm (s, 21-1)
(Synthesis of Compound 6/4-(trimethoxysilyl)benzyl acetate)
##STR00040##
To a 300-ml three-necked flask with a magnetic stirrer, 30.0 g of
sodium acetate and 150.0 g of NMP were added and heated to
130.degree. C. in an oil bath. Then, 90.25 g of
(p-chloromethyl)phenyltrimethoxysilane was added dropwise, and
heating and stirring was performed for 4 hours. The resultant
solution was returned to room temperature and put into a separating
funnel, to which 300 g of toluene and 90 g of water were added to
wash the organic phase. The washing was repeatedly performed three
times. Next, the organic phase was dried with addition of magnesium
sulfate and then filtered, and the solvent was removed by
evaporation to yield a crude product. Subsequently, the crude
product was purified by reduced-pressure distillation to yield 60 g
of 4-(trimethoxysilyl)benzyl acetate of interest.
.sup.1H-NMR (500 MHz, DMSO-d.sub.6): 2.08 ppm (s, 3H), 3.54 ppm (s,
9H), 5.10 ppm (s, 2H), 7.42 ppm (d, 2H), 7.58 ppm (d, 2H)
Synthesis of Compound 7
##STR00041##
To a 300-ml eggplant-shaped flask with a magnetic stirrer, 42.0 g
of 4-bromo-3,5-dimethylphenol (4-BP), 94.6 g of tetrahydrofuran
(THF) (dehydrated) and 1.57 g of pyridinium p-toluenesulfonate
(PPTS) were added and dissolved. To this solution, 22.59 g of ethyl
vinyl ether (EV) was added to allow a reaction to proceed at room
temperature for 20 hours. The solution was neutralized with 0.63 g
of triethylamine (TEA) to prepare a reaction solution A (including
4-(1-ethoxyethoxy)-2,6-dimethylbromobenzene (4-EOEO-2,6-DMePhBr)).
To a 500-ml three-necked flask with a stir bar, 6.09 g of dried
magnesium powder, 0.53 g of iodine, and 189.2 g of tetrahydrofuran
(dehydrated) were added and heated in an oil bath at 60.degree. C.
until the color of iodine was lost. Thereafter, the temperature was
returned to room temperature, and the reaction solution A was added
dropwise at room temperature to allow a reaction to proceed for 2
hours to yield a reaction solution B. To a 1000-ml three-necked
flask with a stir bar, 95.39 g of tetramethoxysilane (TMOS) and
189.2 g of tetrahydrofuran (dehydrated) were added and stirred. At
room temperature, the reaction solution B was added dropwise to
allow a reaction to proceed for 2 hours. After the resultant
solution was concentrated by evaporation, 500 ml of a heptane
solution was added and stirred, followed by filtration. After the
resultant filtrate was concentrated, the product was purified by
reduced-pressure distillation to yield 35 g of
(4-(1-ethoxyethoxy)-2,6-dimethylphenyl)trimethoxysilane of interest
(4-EOEO-2,6-DMePhTMOS).
.sup.1H-NMR (500 MHz, DMSO-d.sub.6): 1.06 ppm (t, 3H), 1.34 ppm (d,
3H), 2.36 ppm (s, 6H), 3.47 ppm (s, 9H), 3.53 ppm (multi, 2H), 5.46
ppm (q, 1H), 6.61 (s, 2H)
Synthesis Example 1
To a 100-ml reaction flask, 0.251 g of a 35% by mass
tetraethylammonium aqueous solution, 0.777 g of water, 7.014 g of
isopropanol, and 3.846 g of tetrahydrofuran were added and stirred.
Then, 5 g (50 mol % in the entire silane) of Compound 3 and 4.157 g
(50 mol % in the entire silane) of
(4-(1-ethoxyethoxy)phenyl)trimethoxysilane were added at room
temperature and heated to 40.degree. C. to allow a reaction to
proceed for 6 hours. The temperature was returned to room
temperature, and 54.942 g of ethyl acetate and 27.471 g of water
were added, and the product was neutralized with a 0.1 N acetic
acid aqueous solution. After the product was put into a separating
funnel and washed with water three times, 25 g of propylene glycol
monomethyl ether acetate was added, and the organic phase was
concentrated to perform solvent displacement. The resultant polymer
corresponds to Formula (3-1) as Polymer 1 and had a molecular
weight of Mw 7200.
Synthesis Example 2
To a 100-ml reaction flask, 0.263 g of a 35% by mass
tetraethylammonium aqueous solution, 0.815 g of water, 7.169 g of
isopropanol, and 3.931 g of tetrahydrofuran were added and stirred.
Then, 5 g (50 mol % in the entire silane) of Compound 1 and 4.360 g
(50 mol % in the entire silane) of
(4-(1-ethoxyethoxy)phenyl)trimethoxysilane were added at room
temperature and heated to 40.degree. C. to allow a reaction to
proceed for 6 hours. The temperature was returned to room
temperature, 56.157 g of ethyl acetate and 28.08 g of water were
added, and the product was neutralized with a 0.1 N acetic acid
aqueous solution. After the product was put into a separating
funnel and washed with water three times, 25 g of propylene glycol
monomethyl ether acetate was added, and the organic phase was
concentrated to perform solvent displacement. The resultant polymer
corresponds to Formula (3-2) as Polymer 2 and had a molecular
weight of Mw 12800.
Synthesis Example 3
To a 100-ml reaction flask, 0.178 g of a 35% by mass
tetraethylammonium aqueous solution, 0.553 g of water, 4.18 g of
isopropanol, and 2.290 g of tetrahydrofuran were added and stirred.
Then, 2.5 g (50 mol % in the entire silane) of Compound 4 and 2.955
g (50 mol % in the entire silane) of
(4-(1-ethoxyethoxy)phenyl)trimethoxysilane were added at room
temperature and heated to 40.degree. C. to allow a reaction to
proceed for 6 hours. The temperature was returned to room
temperature, 32.73 g of ethyl acetate and 16.36 g of water were
added, and the solution was neutralized with a 0.1 N acetic acid
aqueous solution. After the product was put into a separating
funnel and washed with water three times, 25 g of propylene glycol
monomethyl ether acetate was added, and the organic phase was
concentrated to perform solvent displacement. The resultant polymer
corresponds to Formula (3-3) as Polymer 3 and had a molecular
weight of Mw 7300.
Synthesis Example 4
To a 100-ml reaction flask, 0.232 g of a 35% by mass
tetraethylammonium aqueous solution, 0.719 g of water, 6.775 g of
isopropanol, and 7.315 g of tetrahydrofuran were added and stirred.
Then, 5 g (50 mol % in the entire silane) of Compound 5 and 3.844 g
(50 mol % in the entire silane) of
(4-(1-ethoxyethoxy)phenyl)trimethoxysilane were added at room
temperature and heated to 40.degree. C. to allow a reaction to
proceed for 6 hours. The temperature was returned to room
temperature, 53.06 g of ethyl acetate and 26.53 g of water were
added, and the product was neutralized with a 0.1 N acetic acid
aqueous solution. After the product was put into a separating
funnel and washed with water three times, 25 g of propylene glycol
monomethyl ether acetate was added, and the organic phase was
concentrated to perform solvent displacement. The resultant polymer
corresponds to Formula (3-4) as Polymer 4 and had a molecular
weight of Mw 2200.
Synthesis Example 5
To a 100-ml reaction flask, 0.287 g of a 35% by mass
tetraethylammonium aqueous solution, 0.888 g of water, 8.001 g of
isopropanol, and 4.387 g of tetrahydrofuran were added and stirred.
Then, 4 g (35 mol % in the entire silane) of Compound 3, 4.751 g
(50 mol % in the entire silane) of
(4-(1-ethoxyethoxy)phenyl)trimethoxysilane, and 1.695 g (15 mol %
in the entire silane) of
trimethoxy(3-(phenanthren-9-yl)propyl)silane were added at room
temperature and heated to 40.degree. C. to allow a reaction to
proceed for 6 hours. The temperature was returned to room
temperature, 62.67 g of ethyl acetate and 31.34 g of water were
added, and the product was neutralized with a 0.1 N acetic acid
aqueous solution. After the product was put into a separating
funnel and washed with water three times, 25 g of propylene glycol
monomethyl ether acetate was added, and the organic phase was
concentrated to perform solvent displacement. The resultant polymer
corresponds to Formula (3-5) as Polymer 5 and had a molecular
weight of Mw 5200.
Synthesis Example 6
To a 100-ml reaction flask, 0.287 g of a 35% by mass
tetraethylammonium aqueous solution, 0.888 g of water, 7.959 g of
isopropanol, and 4.364 g of tetrahydrofuran were added and stirred.
Then, 4 g (35 mol % in the entire silane) of Compound 3, 4.751 g
(50 mol % in the entire silane) of
(4-(1-ethoxyethoxy)phenyl)trimethoxysilane, and 1.640 g (15 mol %
in the entire silane) of carbazole propyltrimethoxysilane were
added at room temperature and heated to 40.degree. C. to allow a
reaction to proceed for 6 hours. The temperature was returned to
room temperature, 62.34 g of ethyl acetate and 31.17 g of water
were added, and the product was neutralized with a 0.1 N acetic
acid aqueous solution. After the product was put into a separating
funnel and washed with water three times, 25 g of propylene glycol
monomethyl ether was added, and the organic phase was concentrated
to perform solvent displacement. The resultant polymer corresponds
to Formula (3-6) as Polymer 6 and had a molecular weight of Mw
5000.
Synthesis Example 7
To a 100-ml reaction flask, 0.287 g of a 35% by mass
tetraethylammonium aqueous solution, 0.888 g of water, 7.910 g of
isopropanol, and 7.951 g of tetrahydrofuran were added and stirred.
Then, 4 g (35 mol % in the entire silane) of Compound 3, 4.751 g
(50 mol % in the entire silane) of
(4-(1-ethoxyethoxy)phenyl)trimethoxysilane, and 1.575 g (15 mol %
in the entire silane) of
(4-(methylthio)phenoxy)methyltriethoxysilane were added at room
temperature and heated to 40.degree. C. to allow a reaction to
proceed for 6 hours. The temperature was returned to room
temperature, 61.96 g of ethyl acetate and 30.98 g of water were
added, and the product was neutralized with a 0.1 N acetic acid
aqueous solution. After the product was put into a separating
funnel and washed with water three times, 25 g of propylene glycol
monomethyl ether acetate was added, and the organic phase was
concentrated to perform solvent displacement. The resultant polymer
corresponds to Formula (3-7) as Polymer 7 and had a molecular
weight of Mw 5600.
Synthesis Example 8
To a 100-ml reaction flask, 0.287 g of a 35% by mass
tetraethylammonium aqueous solution, 0.888 g of water, 7.750 g of
isopropanol, and 4.318 g of tetrahydrofuran were added and stirred.
Then, 4 g (35 mol % in the entire silane) of Compound 3, 4.751 g
(50 mol % in the entire silane) of
(4-(1-ethoxyethoxy)phenyl)trimethoxysilane, and 1.530 g (15 mol %
in the entire silane) of 8-(3-(trimethoxysilyl)propoxy)quinoline
were added at room temperature and heated to 40.degree. C. to allow
a reaction to proceed for 6 hours. The temperature was returned to
room temperature, 61.96 g of ethyl acetate and 30.98 g of water
were added, and the product was neutralized with a 0.1 N acetic
acid aqueous solution. After the product was put into a separating
funnel and washed with water three times, 25 g of propylene glycol
monomethyl ether was added, and the organic phase was concentrated
to perform solvent displacement. The resultant polymer corresponds
to Formula (3-8) as Polymer 8 and had a molecular weight of Mw
4300.
Synthesis Example 9
To a 100-ml reaction flask, 0.287 g of a 35% by mass
tetraethylammonium aqueous solution, 0.888 g of water, 8.196 g of
isopropanol, and 4.494 g of tetrahydrofuran were added and stirred.
Then, 4 g (35 mol % in the entire silane) of Compound 3, 4.751 g
(50 mol % in the entire silane) of
(4-(1-ethoxyethoxy)phenyl)trimethoxysilane, and 1.949 g (15 mol %
in the entire silane) of
4-methoxy-N-(3-(triethoxysilyl)propyl)benzenesulfonamide were added
at room temperature and heated to 40.degree. C. to allow a reaction
to proceed for 6 hours. The temperature was returned to room
temperature, 64.20 g of ethyl acetate and 32.10 g of water were
added, and the product was neutralized with a 0.1 N acetic acid
aqueous solution. After the product was put into a separating
funnel and washed with water three times, 25 g of propylene glycol
monomethyl ether was added, and the organic phase was concentrated
to perform solvent displacement. The resultant polymer corresponds
to Formula (3-9) as Polymer 9 and had a molecular weight of Mw
4800.
Synthesis Example 10
To a 100-ml reaction flask, 8.88 g of a 35% by mass
tetraethylammonium aqueous solution, 30.72 g of isopropanol, and
30.72 g of tetrahydrofuran were added and stirred. Then, 3.62 g (10
mol % in the entire silane) of Compound 3, 3.01 g (10 mol % in the
entire silane) of (4-(1-ethoxyethoxy)phenyl)trimethoxysilane, and
15.00 g (80 mol % in the entire silane) of methyltriethoxysilane
were added at room temperature and heated to 40.degree. C. to allow
a reaction to proceed for 4 hours. The temperature was returned to
room temperature, 129.81 g of ethyl acetate was added, and the
product was neutralized with a 0.2 N hydrochloric acid aqueous
solution. After the product was put into a separating funnel and
washed with water three times, 25 g of propylene glycol monomethyl
ether acetate was added, and the organic phase was concentrated to
perform solvent displacement. The resultant polymer corresponds to
Formula (3-10) as Polymer 10 and had a molecular weight of Mw
1500.
Synthesis Example 11
To a 100-ml reaction flask, 1.541 g of a 35% by mass
tetraethylammonium aqueous solution, 7.99 g of isopropanol, and
7.99 g of tetrahydrofuran were added and stirred. Then, 0.63 g (10
mol % in the entire silane) of Compound 3 and 5.00 g (90 mol % in
the entire silane) of (3-biphenoxy)methyltriethoxysilane were added
at room temperature and heated to 40.degree. C. to allow a reaction
to proceed for 4 hours. The temperature was returned to room
temperature, 33.77 g of ethyl acetate was added, and the product
was neutralized with a 0.2 N hydrochloric acid aqueous solution.
After the product was put into a separating funnel and washed with
water three times, 25 g of propylene glycol monomethyl ether
acetate was added, and the organic phase was concentrated to
perform solvent displacement. The resultant polymer corresponds to
Formula (3-11) as Polymer 11 and had a molecular weight of Mw
3500.
Synthesis Example 12
To a 100-ml reaction flask, 0.34 g of a 35% by weight
tetraethylammonium aqueous solution, 1.94 g of ultrapure water,
4.13 g of isopropanol, and 4.13 g of tetrahydrofuran were added and
stirred. Then, 6.89 g of Compound 3, 2.36 g of
acetoxymethyltriethoxysilane, and 3.14 g of
(4-(1-ethoxyethoxy)-2,6-dimethylphenyl)trimethoxysilane (compound
7) were added at room temperature and heated to 40.degree. C. to
allow a reaction to proceed for 4 hours. The temperature was
returned to room temperature, 62.00 g of ethyl acetate was added,
and the product was neutralized with a 0.1 N acetic acid aqueous
solution. After the product was put into a separating funnel and
washed with water three times, 30 g of propylene glycol monomethyl
ether acetate was added, and the organic phase was concentrated to
perform solvent displacement. The resultant polymer corresponds to
Formula (3-12) as Polymer 12 and had a molecular weight of Mw
4000.
Synthesis Example 13
To a 100-ml reaction flask, 0.419 g of a 35% by weight
tetraethylammonium aqueous solution, 2.42 g of ultrapure water,
5.45 g of isopropanol, and 5.45 g of tetrahydrofuran were added and
stirred. Then, 8.57 g of Compound 3, 1.53 g of
triethoxy(3-((tetrahydro-2H-pyran-2yl)oxy)propyl)silane, and 6.26 g
of (4-(1-ethoxyethoxy)-2,6-dimethylphenyl)trimethoxysilane
(Compound 7) were added at room temperature and heated to
40.degree. C. to allow a reaction to proceed for 4 hours. The
temperature was returned to room temperature, 82.00 g of ethyl
acetate was added, and the product was neutralized with a 0.1 N
acetic acid aqueous solution. After the product was put into a
separating funnel and washed with water three times, 30 g of
propylene glycol monomethyl ether acetate was added, and the
organic phase was concentrated to perform solvent displacement. The
resultant polymer corresponds to Formula (3-13) as Polymer 13 and
had a molecular weight of Mw 2800.
Synthesis Example 14
To a 100-ml reaction flask, 0.34 g of a 35% by weight
tetraethylammonium aqueous solution, 1.94 g of ultrapure water,
4.13 g of isopropanol, and 4.13 g of tetrahydrofuran were added and
stirred. Then, 6.89 g of Compound 3, 2.36 g of
3-glycidoxypropyltrimethoxysilane, and 3.14 g of
(4-(1-ethoxyethoxy)-2,6-dimethylphenyl)trimethoxysilane (Compound
7) were added at room temperature and heated to 40.degree. C. to
allow a reaction to proceed for 4 hours. The temperature was
returned to room temperature, 62.00 g of ethyl acetate was added,
and the product was neutralized with a 0.1 N acetic acid aqueous
solution. After the product was put into a separating funnel and
washed with water three times, 30 g of propylene glycol monomethyl
ether acetate was added, and the organic phase was concentrated to
perform solvent displacement. The resultant polymer corresponds to
Formula (3-14) as Polymer 14 and had a molecular weight of Mw
3800.
Comparative Synthesis Example 1
To a 100-ml reaction flask, 0.436 g of a 35% by mass
tetraethylammonium aqueous solution, 1.351 g of water, 9.362 g of
isopropanol, and 5.133 g of tetrahydrofuran were added and stirred.
Then, 5.000 g (50 mol % in the entire silane) of
phenyltrimethoxysilane and 7.222 g (50 mol % in the entire silane)
of (4-(1-ethoxyethoxy)phenyl)trimethoxysilane were added at room
temperature and heated to 40.degree. C. to allow a reaction to
proceed for 4 hours. The temperature was returned to room
temperature, 73.33 g of ethyl acetate was added, and the product
was neutralized with a 0.1 N acetic acid aqueous solution. After
the product was put into a separating funnel and washed with water
three times, 25 g of propylene glycol monomethyl ether acetate was
added, and the organic phase was concentrated to perform solvent
displacement. The resultant polymer corresponds to Formula (4-1) as
Polymer 12 and had a molecular weight of Mw 5200.
##STR00042##
Preparation of Curable Resin Composition
The silicon-containing polymers obtained in Synthesis Examples 1 to
14 and Comparative Synthesis Example 1 above, an acid, a curing
catalyst, an additive, and a solvent were mixed in the ratio shown
in Table 1 and filtered through a 0.02 .mu.m fluorocarbon resin
filter to prepare the solutions of curable resin compositions as
film-forming compositions. The proportion of the polymer in Table 1
is shown not by the mass of the polymer solution but by the mass of
the polymer itself.
In Table 1, triphenylsulfonium trifluoromethanesulfonate is denoted
as TPS105, p-toluenesulfonate pyridinium salt is denoted as pPTS,
propylene glycol monomethyl ether acetate is denoted as PGMEA,
propylene glycol monomethyl ether is denoted as PGME, and the
nonionic surfactant manufactured by DIC Corporation is denoted as
R30N (product name). Ultrapure water was used as water. The amount
added is shown by pails by mass.
TABLE-US-00001 TABLE 1 Curing Polymer catalyst Additive Solvent
Example 1 Polymer 1 pPTS PGME PGMEA (parts by mass) 4 0.04 30 70
Example 2 Polymer 2 pPTS PGME PGMEA (parts by mass) 4 0.04 30 70
Example 3 Polymer 3 pPTS PGME PGMEA (parts by mass) 4 0.04 30 70
Example 4 Polymer 4 pPTS PGME PGMEA (parts by mass) 4 0.04 30 70
Example 5 Polymer 5 pPTS PGME PGMEA (parts by mass) 4 0.04 30 70
Example 6 Polymer 6 pPTS PGME PGMEA (parts by mass) 4 0.04 30 70
Example 7 Polymer 7 pPTS PGME PGMEA (parts by mass) 4 0.012 30 70
Example 8 Polymer 8 pPTS TPS105 PGME PGMEA (parts by mass) 4 0.024
0.04 30 70 Example 9 Polymer 9 pPTS TPS105 PGME PGMEA (parts by
mass) 4 0.024 0.12 30 70 Example 10 Polymer 5/Polymer pPTS TPS105
PGME PGMEA (parts by mass) 12 0.024 0.12 30 70 2/2 Example 11
Polymer 10 pPTS R30N PGME PGMEA (parts by mass) 8 0.048 0.04 30 70
Example 12 Polymer 11 pPTS PGME PGMEA (parts by mass) 8 0.24 30 70
Example 13 Polymer 12 pPTS PGME PGMEA (parts by mass) 4 0.04 50 50
Example 14 Polymer 13 pPTS PGME PGMEA (parts by mass) 4 0.04 50 50
Example 15 Polymer 14 pPTS TPS105 PGME PGMEA (parts by mass) 4 0.04
0.04 50 50 Comparative Polymer 12 pPTS PGME PGMEA Example 1 4 0.04
30 70 (parts by mass) Comparative Polymer 12 pPTS PGME PGMEA
Example 2 8 0.24 30 70 (parts by mass)
(Measurement of Optical Constant)
The curable resin compositions prepared in Examples 1 to 15 and
Comparative Examples 1 to 2 were each applied on a silicon wafer
using a spinner. The composition was heated on a hot plate at
215.degree. C. for 1 minute to form a curable resin composition
film (film thickness of 0.05 .mu.m). The refractive index (n value)
and the optical absorption coefficient (k value, which may be
called attenuation coefficient) of the curable resin composition
film were measured using a spectroscopic ellipsometer (manufactured
by J. A. Woollam Co., VUV-VASEVU-302).
(Curability Evaluation)
The curable resin compositions prepared in Examples 1 to 15 and
Comparative Examples 1 to 2 were each applied on a silicon wafer
using a spinner. The composition was heated on a hot plate at
215.degree. C. for 1 minute to form a curable resin composition
film (film thickness of 0.05 .mu.m). Subsequently, the film was
dipped in propylene glycol monomethyl ether acetate. The film
thicknesses before and after dipping were measured, and the one
with a change of 5 nm or more was evaluated as x.
(Lithography Evaluation)
Trade name: EHPE3150 (40.0 g) manufactured by DAICEL CORPORATION,
9-anthracenecarboxylic acid (20.3 g), and benzoic acid (13.7 g)
were dissolved in propylene glycol monomethyl ether (302.0 g), and
then 1.5 g of benzyltriethylammonium was added to allow reflux for
24 hours for a reaction. After the reaction, the solution was
purified using the ion exchange process to obtain a polymer
solution. The resultant polymer (corresponding to Formula (5-1))
was analyzed by GPC, and the weight average molecular weight was
4100 in terms of standard polystyrene.
To 5 g of the resultant polymer solution (the solid content of the
polymer is 16% by mass), 0.2 g of tetramethoxymethyl glycol uril,
0.03 g of pyridinium-p-toluenesulfonate, 0.0008 g of MEGAFACE
[registered trademark] R-30 (manufactured by DIC Corporation (the
former Dainippon Ink and Chemicals, Inc.), trade name), 6.4 g of
propylene glycol monomethyl ether, and 4.5 g of propylene glycol
monomethyl ether acetate were mixed to form a solution.
Subsequently, the solution was filtered using a polyethylene
microfilter with a pore size of 0.10 .mu.m and further filtered
using a polyethylene microfilter with a pore size of 0.05 .mu.m to
prepare a solution of the organic resist underlayer film-forming
composition for use in the lithography process with multilayer
films.
##STR00043##
The organic resist underlayer film-forming composition was applied
on a silicon wafer and baked on a hot plate at 240.degree. C. for
60 seconds to obtain an organic resist underlayer film having a
film thickness of 200 nm. The curable resin compositions prepared
in Examples 1 to 10, Examples 13 to 15 and Comparative Example 1
were each applied thereon using a spinner. Subsequently, the resin
composition was baked on a hot plate at 215.degree. C. for 1 minute
to form a curable resin film (film thickness of 0.08 pun). A
commercially available photoresist solution (manufactured by TOKYO
OHKA KOGYO CO., LTD., trade name: TDUR-P3435LP) was applied thereon
using a spinner and heated on a hot plate at 90.degree. C. for 1
minute to form a photo resist film (film thickness of 0.25 .mu.m).
Then, using an NSR-S205C lens scanning-type stepper (wavelength 248
nm, NA: 0.75, .sigma.: 0.85 (CONVENTIONAL)) manufactured by Nikon
Corporation, exposure was performed through a mask set such that
the photoresist pattern after development has a line width and a
line-to-line width of 0.16 .mu.m. Subsequently, "post exposure
bake" was performed on a hot plate at 110.degree. C. for 1 minute.
After cooling, development was performed using a 2.38%
tetramethylammonium hydroxide aqueous solution as a developer. The
resist bottom shape of the resultant pattern was evaluated by SEM.
Those with a rectangular resist shape are evaluated as straight,
and those with no resultant pattern or with loss of rectangularity
are evaluated as pattern failure.
(Filling Evaluation)
As shown in FIG. 1, the curable resin compositions of Examples 1 to
15 and Comparative Examples 1 to 2 were each applied on an uneven
substrate 2 using a spin coater and then heated on a hot plate at
215.degree. C. for 1 minute to form a curable resin film 1 having a
film thickness of 180 nm. The uneven substrate used had a hole
pattern formed of CVD-TEOS with a height of 300 nm and a minimum
width of 20 nm. The hole-filling characteristic was then evaluated
by observing the hole-filling shape (embeddability) in the
resultant substrate through cross section SEM. Those with no voids
and exhibiting high embeddability were evaluated as good.
TABLE-US-00002 TABLE 2 Refractive index n with wavelength of 248
nm, optical absorption coefficient and curability evaluation,
hole-filling characteristic n/k (248 Curability Lithography
Hole-filling nm) evaluation evaluation characteristic Example 1
1.87/0.08 .largecircle. Straight Good Example 2 1.87/0.05
.largecircle. Straight Good Example 3 1.83/0.02 .largecircle.
Straight Good Example 4 1.82/0.02 .largecircle. Straight Good
Example 5 1.79/0.22 .largecircle. Straight Good Example 6 1.86/0.18
.largecircle. Straight Good Example 7 1.86/0.10 .largecircle.
Straight Good Example 8 1.89/0.18 .largecircle. Straight Good
Example 9 1.87/0.11 .largecircle. Straight Good Example 10
1.81/0.11 .largecircle. Straight Good Example 13 1.83/0.10
.largecircle. Straight Good Example 14 1.88/0.10 .largecircle.
Straight Good Example 15 1.79/0.08 .largecircle. Straight Good
Comparative 1.83/0.01 X Pattern failure -- Example 1
TABLE-US-00003 TABLE 3 Refractive index n with wavelength of 633
nm, curability evaluation Curability Hole-filling n (633 nm)
evaluation characteristic Example 11 1.480 .largecircle. Good
Example 12 1.618 .largecircle. Good Comparative 1.570 X -- Example
2
INDUSTRIAL APPLICABILITY
The film-forming composition of the present invention has high
curability and has high embeddability for an uneven substrate. In
addition, in the use for a resist underlayer film for use in the
lithography process for semiconductor manufacturing using
multilayer films, or for silicon hard masks, satisfactory shapes
can be achieved after exposure, development, and etching.
The present invention can be used as a film-forming composition
having favorable effects such as curability and embeddability and a
resist underlayer film for use in the lithography process for
semiconductor devices.
DESCRIPTION OF THE REFERENCE NUMERALS
1 Curable resin film 2 Uneven substrate
* * * * *